Compound and polymer compound containing the compound

ABSTRACT

Provided is a compound having higher fluorescence quantum yield and higher optical stability than a conventional FLAP and a polymer compound containing the compound. 
     
       
         
         
             
             
         
       
         
         
           
             A: seven or eight-membered ring structure, 
             Y 1 ,Y 2 ,Y 3 : halogen atom or the like, 
             a1: number of Y 1 , a2: number of Y 2 , 
             B: number of Y 3 , 
             0≤m and n≤3: when 1≤m≤3, Y 1  may be substituted with a structure portion defined by m, when 1≤n≤3, Y 2  may be substituted with a structure portion defined by n, and 
             B 1 , B 2 : Formulas (2-1) to (2-3). 
           
         
       
    
     
       
         
         
             
             
         
       
         
         
           
             C 1 , C 2 , C 3 : structure containing a cyclic hydrocarbon compound, 
             D 1 , D 2 , D 3 : substructure that inhibits aggregation, 
             E 1 , E 2 , E 3 : polymerizable substructure, 
             Z 1 : hydrogen atom or the like, 
             c: number of substituent groups Z 1 , 
             Z 2 , Z 3 : hydrogen atom or the like, and may form a ring with C 2 .

TECHNICAL FIELD

The present invention relates to a compound and a polymer compoundcontaining the compound, in particular, relates to a polymer compoundcontaining a compound that can visualize stress (Flexible AromaticPhotofunctional molecules, hereinafter, which may be denoted to as“FLAP”) and a polymer compound containing the FLAP.

BACKGROUND ART

Functional materials have been developed for various uses in accordancewith the characteristics of the functional material, and as an examplethereof, attempts to visualize mechanical stress such as compression,expansion, bending, or the like applied on a material have been made.

As a method for visualizing mechanical stress, visualization usingdispersion of excimers (see Non-Patent Literature 1), visualizationusing binding cleavage of chromatic molecules (see Non-Patent Literature2), visualization using energy transform of chemical light emission (seeNon-Patent Literature 3), visualization using emission of smallmolecules (see Non-Patent Literature 4), and the like are known.

Further, a mechanochromic material made of a polymer having a repetitionunit of a urethane structure or an ester structure in whichdiarylbibenzofuranone structure is urethane-bound or ester-bound isknown (see Patent Literature 1).

Synthetic π-conjugated molecules have been used as a composition of dyesor pigments, aromatic polymers, or optical storage material for a longtime and, in recent years, have been widely and practically used as aform of organic EL photodynamic therapy agents, fluorescent probes, orthe like. In general, since synthetic π-conjugated molecules are made ofrigid aromatic rings and multiple bonds (mainly, sp² carbon), asignificant majority of them necessarily have rigid structure.

Such rigid structure has many advantages also in the physical property,for example, an intended shape of a molecular framework can besynthesized, and because of small structure deformation, the structureexhibits a slow non-radiometric deactivation process and high lightemission efficiency. On the other hand, it can also be considered that arigid fundamental molecular framework makes it difficult to transformthe physical property caused by flexibility of the structure in asimilar manner to an inorganic material, and only the expression of astatic physical property is reached. Thus, the present inventors createa compound having condensed-ring luminescent anthraceneimide as tworigid “wings” at opposed positions of flexible conjugated eight-memberedring (cyclooctatetraene) as illustrated in FIG. 1A. This compoundexhibits inversion behavior between a V-form and a Λ-form in response tothe motion of the eight-membered ring and emits blue light in a V-formstate and green light in a planar state due to a change of electronicstructure involved by the motion of the steric structure, as illustratedin FIG. 1B (see Non-Patent Literatures 5 and 6).

By using the compound described above, it is possible to visuallyindicate the degree of a mechanical stimulation (mechanical stress)applied on a material by means of a change of the light emission color.As a visualization technology using the compound described above, forexample, the present inventors have found that, by dispersing thecompound described above in an adhesive agent, it is possible tovisualize curing process of the adhesive agent and, in addition,determine a portion of insufficient curing in a contactless manner (seePatent Literature 2).

Further, the present inventors have found (i) that, since amechanochromic resin in which a mechanochromic light-emitting materialrepresented by the following Formula (P1) or (P2) is cross-linked to apolymer chain changes the light emission color thereof quickly andreversibly due to expansion and compression, stress applied to amaterial can be visualized in real time and (ii) that, althoughsynthesis of a mechanochromic resin is difficult with mere introductionof a polymerizable group to anthraceneimide dimers or naphthaleneimidedimers disclosed in Non-Patent Literatures 5 to 7, a mechanochromicresin in which a mechanochromic light-emitting material is cross-linkedcan be synthesized by introducing substituent group that inhibitsaggregation between anthraceneimide dimers or naphthaleneimide dimersand the polymerizable group (see Patent Literature 3).

(In the formula, Y₁ and Y₂ denote substituent groups that inhibitaggregation of a mechanochromic light-emitting material expressed byFormula (1) and may be the same or may be different. Z₁ and Z₂ denotepolymerizable groups and may be the same or may be different. Note thatelements Y₁ and Y₂ and elements Z₁ and Z₂ in Formulas (P1) and (P2) aredifferent from elements Y₁ and Y₂ and an element Z of the presentinvention described later.)

CITATION LIST Patent Literature

-   Patent Literature 1: Japanese Patent Application Publication No.    2014-58606-   Patent Literature 2: Japanese Patent Application Publication No.    2015-113312-   Patent Literature 3: International Publication No. WO2016/080358

Non-Patent Literature

-   Non-Patent Literature 1: Christoph Weder et al.,    “Deformation-Induced Color Changes in Melt-Processed    Photoluminescent Polymer Blends”, Chem Mater, 2003, 15, p 4717-4724-   Non-Patent Literature 2: N. R. Sottos et al., “Force-induced    activation of covalent bonds in mechanoresponsive polymeric    materials”, Nature, 2009, Vol. 459, p 68-72-   Non-Patent Literature 3: R. P. Sijbesma et al., “Mechanically    induced chemiluminescence from polymers incorporating a    1,2-dioxetane unit in the main chain”, Nature Chem, 2012, Vol. 4, p    559-562-   Non-Patent Literature 4: Stephen L. Craig et al., “Mechanochemical    Activation of Covalent Bonds in Polymers with Full and Repeatable    Macroscopic Shape Recovery”, ACS Macro Lett, 2014, 3, p 216-219-   Non-Patent Literature 5: S. Saito et al., “A π-Conjugated System    with Flexibility and Rigidity That Shows Environment-Dependent RGB    Luminescence”, Journal of the American Chemical Society, 2013, 135,    p 8842-8845-   Non-Patent Literature 6: S. Saito et al., “Hybridization of a    Flexible Cyclooctatetraene Core and Rigid Aceneimide Wings for    Multiluminescent FLAPping π Systems”, Chemistry—A European Journal,    2014, 20, p 2193-2200-   Non-Patent Literature 7: Shouhei Saito, Shigehiro Yamaguchi, “Move    π-conjugated Framework to Cause Expression of Function”, CHEMISTRY,    Vol. 69, No. 5 (2014), p 32-37

SUMMARY OF INVENTION Technical Problem to be Solved by the Invention

When the FLAP is applied to a sensor or the like, higher spatialresolution in distortion detection is preferable. Thus, there is ademand for a molecule having higher fluorescence quantum yield andhigher optical stability than the conventional FLAP.

The present invention has been made to solve the problems describedabove and intends to provide a compound having high fluorescence quantumyield and high optical stability and a polymer compound containing thecompound.

Solution to Problem

The present invention is directed to a compound and a polymer compoundcontaining the compound described below.

[1]

A compound represented by a following general Formula (1):

wherein in general Formula (1),

A denotes a seven-membered ring or eight-membered ring structure thatmay have a substituent group and forms a conjugated system with abenzene ring bound to A,

Y¹ and Y² each denote, independently, a substituent group selected froma halogen atom, an aliphatic hydrocarbon group with 1-20 carbons thatmay have a substituent group, an aryl group with 6-20 carbons that mayhave a substituent group, an alkoxy group with 1-10 carbons that mayhave a substituent group, an cyano group, and a heterocyclic compoundgroup having 5-8 atoms forming a ring, and when a plurality ofsubstituent groups Y¹ and Y² are provided, respective substituent groupsmay be the same as each other or may be different from each other,

a1 denotes the number of the substituent groups Y¹, and a2 denotes thenumber of the substituent groups Y²,

Y³ denotes a substituent group selected from a halogen atom, an alkylgroup with 1-20 carbons that may have a substituent group, an alkynylgroup with 2-20 carbons that may have a substituent group, an aryl groupwith 6-20 carbons that may have a substituent group, an alkoxy groupwith 1-10 carbons that may have a substituent group, a carboxylic acidester group with 2-20 carbons that may have a substituent group, acarboxyl group, a hydroxyl group, and a cyano group, when a plurality ofsubstituent groups Y³ are provided, respective substituent groups may bethe same as each other or may be different from each other,

b denotes the number of the substituent groups Y³,

m and n each denote, independently, an integer greater than or equal to0 and less than or equal to 3, when m is an integer greater than orequal to 1 and less than or equal to 3, Y¹ may be substituted with astructure portion defined by m, and similarly, when n is an integergreater than or equal to 1 and less than or equal to 3, Y² may besubstituted with a structure portion defined by n, and

B¹ and B² each denote, independently, any of the structures representedby general Formulas (2-1) to (2-3):

wherein in general Formulas (2-1) to (2-3),

C¹ denotes a structure containing a cyclic hydrocarbon compound,

C² and C³ each denote a structure containing a cyclic hydrocarboncompound but may have no structure containing a cyclic hydrocarboncompound, and when C² and C³ have no structure containing a cyclichydrocarbon compound, D², D³, E², and E³ are arranged in a framework ofa compound represented by general Formula (1),

D¹, D², and D³ each denote a substructure that inhibits aggregation,

E¹, E², and E³ each denote a polymerizable substructure,

Z¹ each denote, independently, a substituent group selected from ahydrogen atom, a halogen atom, an alkyl group with 1-20 carbons that mayhave a substituent group, an alkynyl group with 2-20 carbons that mayhave a substituent group, an aryl group with 6-20 carbons that may havea substituent group, an alkoxy group with 1-10 carbons that may have asubstituent group, and a cyano group and may form a ring with C¹, andwhen a plurality of substituent groups Z¹ are provided, respectivesubstituent groups may be the same as each other or may be differentfrom each other,

c denotes the number of substituent groups Z¹, and

Z² and Z³ each denote, independently, a substituent group selected froma hydrogen atom, a halogen atom, an alkyl group with 1-20 carbons thatmay have a substituent group, an alkynyl group with 2-20 carbons thatmay have a substituent group, an aryl group with 6-20 carbons that mayhave a substituent group, an alkoxy group with 1-10 carbons that mayhave a substituent group, and a cyano group, and Z² and Z³ may each forma ring with C², independently.

[2]

The compound according to [1] above, wherein in the general Formula (1),the A is represented by general Formula (3) or (4):

wherein in general Formula (4), Q denotes an 0 atom, an S atom, a Seatom, or an N atom or a P atom having an alkyl group as a substituentgroup.

[3]

The compound according to [1] or [2] above, wherein in the generalFormula (1), the B¹ and B² have any structure of general Formulas (5-1)to (5-3):

wherein Z⁴ in general Formula (5-2) is the same as the Z² and Z³.

[4]

The compound according to any one of [1] to [3] above, wherein the E¹,E², and E³ each denote a polymerizable substituent group.

[5]

The compound according to any one of [1] to [4] above, wherein the D¹,D², and D³ have any of following structures:

wherein R₁ to R₇ each denote H, a linear, branched, or cyclic alkylgroup with 1-20 carbons, an aryl group with 6-20 carbons, F, Cl, Br, I,CF₃, CCl₃, CN, or OCH₃, and R₁ to R₇ may be the same or different.

[6]

The compound according to any one of [1] to [5] above, wherein the E¹,E², and E³ are any of the Formulas (E-1) to (E-18):

wherein in the Formulas (E-12) and (E-13), X denotes amide or ester butmay not be included, R₁ in the Formulas (E-12) and (E-13) is the same asR₁ according to claim 5, R in Formulas (E-1) to (E-18) denotes a linear,branched, or cyclic alkyl group with 1-20 carbons or an aryl group with6-20 carbons, R in Formulas (E-1) to (E-11) may not be included, andeach filled circle represents D¹, D², or D³.

[7]

The compound according to [3] above, wherein in the general Formula (1),the B¹ and B² have any of structures of the general Formulas (5-1) and(5-2).

[8]

The compound according to [3] above, wherein in the general Formula (1),the B¹ and B² have a structure of the general Formula (5-3), and whereinm and n of a compound represented by the general Formula (1) are 0 or 3.

[9]

The compound according to any one of [1] to [8] above, wherein in thegeneral Formula (1),

the a1

denotes an integer of 0 to 3 when m is 0, and

denotes an integer that Y¹ can be substituted in accordance with thenumber 0 to m when m is an integer greater than or equal to 1 and lessthan or equal to 3,

the a2

denotes an integer of 0 to 3 when n is 0, and

denotes an integer that Y² can be substituted in accordance with thenumber 0 to n when n is an integer greater than or equal to 1 and lessthan or equal to 3, and

the b denotes an integer greater than or equal to 0 and less than orequal to 4,

[10]

The compound according to any one of [2] to [9] above, wherein in thegeneral Formula (1), the A is the general Formula (4).

[11]

The compound according to any one of [1] to [10] above, wherein in thegeneral Formula (1), the b is an integer greater than or equal to 1 andless than or equal to 4.

[12]

A polymer compound made by polymerizing the compound described in anyone of [1] to [11] above.

[13]

The polymer compound according to [12] above, wherein the compound isbound to the polymer compound via a urethane binding in the polymercompound.

[14]

The polymer compound according to [12] or [13] above further comprising,in a main chain of the polymer compound, a chemical structure includedin the compound.

[15]

The polymer compound according to [12] or [13] above further comprisinga cross-linked site made of a chemical structure included in thecompound.

Advantageous Effect of Invention

With a use of the compound of the present invention, fluorescencequantum yield can be increased, and optical stability is improved.

BRIEF DESCRIPTION OF DRAWINGS

FIG. 1A and FIG. 1B illustrate a compound having condensed-ringluminescent anthraceneimide as two rigid “wings” at opposed positions offlexible conjugated eight-membered ring (cyclooctatetraene) disclosed inNon-Patent Literature 5.

FIG. 2A and FIG. 2B illustrate examples including a FLAP in the mainchain of a polymer.

FIG. 3A and FIG. 3B illustrate examples including a FLAP as across-linkage point of a polymer.

FIG. 4A and FIG. 4B illustrate other examples including a FLAP as across-linkage point of a polymer.

FIG. 5 is a graph illustrating a result of fluorescence attenuationmeasured in Example 5 and Comparative example 1.

FIG. 6 is a graph illustrating a result of fluorescence attenuationmeasured in Example 6.

FIG. 7 is a graph illustrating a result of fluorescence attenuationmeasured in Comparative example 2.

DESCRIPTION OF EMBODIMENTS

Embodiments of a compound (FLAP) and a polymer compound containing thecompound will be specifically described below.

First, in the present invention, “FLAP” means a compound that canvisualize stress because the light emission wavelength changes due tomechanical stress and the light emission color changes.

The compound (FLAP) of the present invention is represented by thefollowing Formula (1).

Symbols in the above general Formula (1) are defined as follows.

Symbol A denotes a seven-membered ring structure or an eight-memberedring structure that may have a substituent group and forms a conjugatedsystem with a benzene ring bound to A.

Symbols Y¹ and Y² each denote, independently, a substituent groupselected from a halogen atom, an aliphatic hydrocarbon group with 1-20carbons that may have a substituent group, an aryl group with 6-20carbons that may have a substituent group, an alkoxy group with 1-10carbons that may have a substituent group, an cyano group, and aheterocyclic compound group having 5-8 atoms forming a ring. When aplurality of substituent groups Y¹ and Y² are provided, respectivesubstituent groups may be the same as each other or may be differentfrom each other.

Symbol a1 denotes the number of the substituent groups Y¹, and symbol a2denotes the number of the substituent groups Y².

Symbol Y³ denotes a substituent group selected from a halogen atom, analkyl group with 1-20 carbons that may have a substituent group, analkynyl group with 2-20 carbons that may have a substituent group, anaryl group with 6-20 carbons that may have a substituent group, analkoxy group with 1-10 carbons that may have a substituent group, acarboxylic acid ester group with 2-20 carbons that may have asubstituent group, a carboxyl group, a hydroxyl group, and a cyanogroup. When a plurality of substituent groups Y³ are provided,respective substituent groups may be the same as each other or may bedifferent from each other.

Symbol b denotes the number of the substituent groups Y³. Symbol bdenotes an integer greater than or equal to 0 and less than or equal to4.

Symbol m and n each denote, independently, an integer greater than orequal to 0 and less than or equal to 3. Note that, when m is an integergreater than or equal to 1 and less than or equal to 3, Y¹ may besubstituted with a structure portion defined by m. Similarly, when n isan integer greater than or equal to 1 and less than or equal to 3, Y²may be substituted with a structure portion defined by n.

Note that, when m is an integer greater than or equal to 1 and less thanor equal to 3, a1 denotes an integer that Y¹ can be substituted inaccordance with the number 0 to m. When m is 0, a1 denotes an integer of0 to 3.

Further, when n is an integer greater than or equal to 1 and less thanor equal to 3, a2 denotes an integer that Y² can be substituted inaccordance with the number 0 to n. When n is 0, a2 denotes an integer of0 to 3.

Symbols B¹ and B² each denote, independently, any of the structuresrepresented by the following general Formulas (2-1) to (2-3). Note thatthe double bond at the right end of the structure represented by thefollowing general Formulas (2-1) to (2-3) corresponds to the double bondat the right end of B¹ of the compound and the double bond at the leftend of B² of the compound represented by the above general Formula (1).

Symbols in general Formulas (2-1) to (2-3) are defined as follows.

Symbol C¹ denotes a structure containing a cyclic hydrocarbon compound.

Symbols C² and C³ each denote a structure containing a cyclichydrocarbon compound but may have no structure containing a cyclichydrocarbon compound. When C² and C³ have no structure containing acyclic hydrocarbon compound, D², D³, E², and E³ are arranged in aframework of a compound represented by general Formula (1).

Symbols D¹, D², and D³ each denote a substructure that inhibitsaggregation.

Symbols E¹, E², and E³ each denote a polymerizable substructure.

Note that, while D¹ to D³ and E¹ to E³ may be arranged in C¹ to C³,respectively, E¹ to E³ may be bound to D¹ to D³.

Symbols Z¹ each denote, independently, a substituent group selected froma hydrogen atom, a halogen atom, an alkyl group with 1-20 carbons thatmay have a substituent group, an alkynyl group with 2-20 carbons thatmay have a substituent group, an aryl group with 6-20 carbons that mayhave a substituent group, an alkoxy group with 1-10 carbons that mayhave a substituent group, and a cyano group and may form a ring with C¹.When a plurality of substituent groups Z¹ are provided, respectivesubstituent groups may be the same as each other or may be differentfrom each other.

Symbol c denotes the number of substituent groups Z¹. Symbol c denotesan integer greater than or equal to 1 and less than or equal to 4.

Symbols Z² and Z³ each denote, independently, a substituent groupselected from a hydrogen atom, a halogen atom, an alkyl group with 1-20carbons that may have a substituent group, an alkynyl group with 2-20carbons that may have a substituent group, an aryl group with 6-20carbons that may have a substituent group, an alkoxy group with 1-10carbons that may have a substituent group, and a cyano group. Symbols Z²and Z³ may each form a ring with C², independently.

In the above general Formula (1), A is not particularly limited as longas the electronic structure changes due to conformation(three-dimensional positional relationship of constituent atoms) changeto form a π-conjugated system and may be, for example, an eight-memberedring represented by the following general Formula (3) or aseven-membered ring represented by the following general Formula (4).

In the above general Formula (4), symbol Q denotes an O atom, an S atom,a Se atom, or an N atom or a P atom having an alkyl group as asubstituent group. Q is preferably 0 atom, an S atom, or an N atom or aP atom having an alkyl group as a substituent group, more preferably 0atom or an N atom having an alkyl group, and much more preferably an Oatom.

The above aliphatic hydrocarbon group with 1-20 carbons that may have asubstituent group described for Y² and Y² is not particularly limitedand may be an alkyl group, an alkenyl group, an alkynyl group or thelike with 1-20 carbons, and preferably an alkyl group with 1-20 carbonsor an alkynyl group with 2-20 carbons.

With respect to the alkyl group with 1-20 carbons that may have thesubstituent group described for the above Y¹, Y², Y³, Z¹, Z², and Z³,the alkyl group with 1-20 carbons may be any form of a straight chain, abranch, or a ring and may be, as a specific example, methyl, ethyl,n-propyl, 2-propyl, n-butyl, 1-methylpropyl, 2-methylpropyl, tert-butyl,n-pentyl, 1-methylbutyl, 1-ethylpropyl, tert-pentyl, 2-methylbutyl,3-methylbutyl, 2,2-dimethylpropyl, n-hexyl, 1-methylpentyl,1-ethylbutyl, 2-methylpentyl, 3-methylpentyl, 4-methylpentyl,2-methylpentane-3-yl, 3,3-dimethylbutyl, 2,2-dimethylbutyl,1,1-dimethylbutyl, 1,2-dimethylbutyl, 1,3-dimethylbutyl2,3-dimethylbutyl, 1-ethylbutyl, 2-ethylbutyl, heptyl, octyl, nonyl,decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl,heptadecyl, octadecyl, nonadecyl, equosyl, cyclopropyl, cyclobutyl,cyclopentyl, cyclohexyl, or the like, for example. Among the alkylgroups described above, the alkyl group with 1-16 carbons is preferable.Further, a substituent group may be phenyl, mesityl,2,6-diisopropylphenyl, 3,5-di(tert-butyl)phenyl, 4-tert-butylphenyl, orthe like.

With respect to the alkynyl group with 6-20 carbons that may have thesubstituent group described for the above Y¹, Y², Y³, Z¹, Z², and Z³,the alkynyl group may be ethynyl group, 1-propynyl group, 1-butynylgroup, 1-pentinyl group, 1-hexynyl group, 1-heptynyl group, 1-octinylgroup, 1-nonynyl group, 1-decynyl group, 1-undecynyl group, 1-dodecynylgroup, 1-tridecynyl group, 1-tetradecynyl group, 1-pentadecynyl group,1-hexadecynyl group, 1-heptadecynyl group, 1-octadecynyl group,1-nonadecynyl group, 1-icosynyl group, 1-henicosynyl group, 1-docosynylgroup, 1-tricosynyl group, 1-tetracosynyl group, 1-pentacosynyl group,1-hexacosynyl group, 1-heptacosynyl group, 1-octacosynyl group,1-nonacosynyl group, and 1-triakontinyl group. Preferably, the alkynylmay be ethynyl group, 1-propynyl group, 1-butynyl group, 1-pentinylgroup, 1-hexynyl group, 1-heptynyl group, 1-octinyl group, 1-nonynylgroup, 1-decynyl group, 1-undecynyl group, 1-dodecynyl group,1-tridecynyl group, 1-tetradecynyl group, 1-pentadecynyl group,1-hexadecynyl group, 1-heptadecynyl group, 1-octadecynyl group,1-nonadecynyl group, 1-icosynyl group, and the like. A specific exampleof the substituent group may be trimethylsilyl, triethylsilyl,triisopropylsilyl, triphenylsilyl, tert-butyl-dimethylsilyl,tert-butyl-diphenylsilyl, phenyl, mesityl, 2,6-diisopropylphenyl,3,5-di(tert-butyl)phenyl, 4-tert-butylphenyl, or the like.

With respect to the aryl group with 6-20 carbons that may have thesubstituent group described for the above Y¹, Y², Y³, Z¹, Z², and Z³, aspecific example of the aryl group with 6-20 carbons may be phenyl,indenyl, pentalenyl, naphthyl, azulenyl, fluorenyl, phenanthrenyl,anthracenyl, acenaphthylenyl, biphenylenyl, naphthacenyl, pyrenyl, orthe like. Note that the substituent group may be the same as thesubstituent group of the above alkyl group with 1-20 carbons.

With respect to the alkoxy group with 1-10 carbons that may have thesubstituent group described for the above Y¹, Y², Y³, Z¹, Z², and Z³, aspecific example of the alkoxy group with 1-10 carbons may be methoxygroup, ethoxy group, propoxy group, isopropoxy group, butoxy group,isobutoxy group, tert-butoxy group, pentyloxy group, hexyloxy group,cyclohexyloxy group, heptyloxy group, octyloxy group, 2-ethylhexyloxygroup, nonyloxy group, decyloxy group, or the like. Note that thesubstituent group may be the same as the substituent group of the abovealkyl group with 1-20 carbons.

With respect to the heterocyclic compound group having 5-8 atoms forminga ring described for the above Y¹ and Y², a specific example may bepyrrolidine, tetrahydrofuran, tetrahydrothiophene, pyrrole, furan,thiophene, piperidine, tetrahydropyran, tetrahydrothiopyran, pyridine,pyrillium ion, thiapyran, hexamethyleneimine, hexamethylene oxide,hexamethylene sulfide, azatropyridene, oxycycloheptatriene,thiotropyridene, imidazole, pyrazole, oxazole, triazole, imidazoline,dioxane, morpholine, thiazine, triazole, tetrazole, dioxolane,pyridazine, pyrimidine, pyrazine, or the like.

With respect to the carboxylic acid ester group with 2-20 carbons thatmay have a substituent group described for the above Y³, a specificexample of the carboxylic acid ester group may be carboxylic acid methylester group, carboxylic acid ethyl ester group, carboxylic acid propylester group, carboxylic acid butyl ester group, or the like. Note thatthe substituent group may be the same as the substituent group of theabove alkyl group with 1-20 carbons.

With respect to the above Y¹, Y², Y³, Z¹, Z², and Z³, any combination bywhich aggregation of the synthesized FLAP is inhibited may be employed,and the combination having a solubility that enables sufficientdissolution to a solvent is preferable. In terms of the above, a smallernumber of substituent groups described above is preferable, and acompound having none of the above Y¹, Y², Y³, Z¹, Z², and Z³,specifically, having no substituent group is preferable.

Note that, in the above general Formula (4), a specific chemicalsubstructure when one Y³ described above is provided (that is, b=1) maypreferably be, for example, a ring structure (4-1) as included in amethylated dibenzoxepine based compound, a ring structure (4-2) asincluded in an AT-methylated dibenzoazepine based compound, or the likeas described below.

Further, a more specific example of any of the structures represented bythe above general Formulas (2-1) to (2-3) may be any of the structuresof the following general Formulas (5-1) to (5-3).

Z⁴ in the above general Formula (5-2) is the same as the above Z² andZ³.

A specific example of each substructure of the above D¹, D², and D³ thatinhibits aggregation may be the structure described below. Note that,since the substructure that inhibits aggregation can suppressaggregation of a compound (FLAP) in a solution, reaction forcross-linkage to a polymer chain or introduction of the compound (FLAP)into a polymer chain becomes easier.

Symbols R₁ to R₇ of the above substructure that inhibits aggregationeach denote H, a linear, branched, or cyclic alkyl group with 1-20carbons, an aryl group with 6-20 carbons, F, Cl, Br, I, CF₃, CCl₃, CN,or OCH₃. R₁ to R₇ may be the same or different. Note that the linear,branched, or cyclic alkyl group with 1-20 carbons and the aryl groupwith 6-20 carbons are the same as the specific example described for theabove Y¹, Y₂, Y³, Z¹, Z², and Z³.

A specific example of the polymerizable substituent group denoted as theabove E¹, E², and E³ may be (E-1) to (E-18) represented below.

While R in Formulas (E-1) to (E-18) denotes a linear, branched, orcyclic alkyl group with 1-20 carbons or an aryl group with 6-20 carbons,R in Formulas (E-1) to (E-13) may not be included. Each symbol • (filledcircle) represents D², D², or D³.

Each substituent group represented by the above Formulas (E-1) to (E-7)is a monomer for polyaddition and polycondensation reaction. The monomerrepresented by (E-1) may be hydroxymethyl, hydroxyethyl, hydroxypropyl,hydroxybutyl, hydroxypentyl, hydroxyhexyl, hydroxycyclopropyl,hydroxyphenyl, or the like. The monomer represented by (E-2) may becarboxymethyl, carboxyethyl, carboxypropyl, carboxybutyl, carboxypentyl,carboxyhexyl, carboxycyclopropyl, carboxyphenyl, or the like. Themonomer represented by (E-3) may be aminomethyl, aminoethyl,aminopropyl, aminobutyl, aminopentyl, aminohexyl, aminocyclopropyl,aminophenyl, or the like. The monomer represented by the above Formula(E-4) may be methyl isocyanate, ethyl isocyanate, propyl isocyanate,butyl isocyanate, pentyl isocyanate, hexyl isocyanate, cyclopropylisocyanate, phenyl isocyanate, or the like. The monomer represented by(E-5) may be methyl isothiocyanate, ethyl isothiocyanate, propylisothiocyanate, butyl isothiocyanate, pentyl isothiocyanate, hexylisothiocyanate, cyclopropyl isothiocyanate, phenyl isothiocyanate, orthe like. The monomer represented by the above Formula (E-6) is amonomer resulted by activating a general ester by N-hydroxysuccinimide(NHS) and may be methyl NHS ester, ethyl NHS ester, propyl NHS ester,butyl NHS ester, pentyl NHS ester, hexyl NHS ester, cyclopropyl NHSester, phenyl NHS ester, or the like. The monomer represented by theabove Formula (E-7) may be glycidyl, ethyl epoxy, propyl epoxy, butylepoxy, pentyl epoxy, hexyl epoxy, cyclopropyl epoxy, phenyl epoxy, orthe like.

Each substituent group represented by the above Formulas (E-8) to (E-11)is a click-reaction monomer. The monomer represented by the aboveFormula (E-8) may be methylacetylene, ethylacetylene, propylacetylene,butylacetylene, pentylacetylene, hexylacetylene, cyclopropylacetylene,phenylacetylene, or the like. The monomer represented by the aboveFormula (E-9) may be methyl azide, ethyl azide, propyl azide, butylazide, pentyl azide, hexyl azide, cyclopropyl azide, phenyl azide, orthe like. The monomer represented by the above Formula (E-10) may bemethylthiol, ethylthiol, propylthiol, butylthiol, pentylthiol,hexylthiol, cyclopropylthiol, thiophenol, or the like. The monomerrepresented by the above Formula (E-11) may be vinyl, ethyl vinyl,propyl vinyl, butyl vinyl, pentyl vinyl, hexyl vinyl, cyclopropyl vinyl,phenyl vinyl, maleimide, or the like. Note that, in the case of clickreaction, azide and alkynes are reacted, and vinyl and thiol arereacted. Therefore, when the monomer of Formula (E-8) is used as apolymerizable group, the polymerizable monomer forming a polymer chaindescribed later can use a monomer having azide. Similarly, apolymerizable monomer having alkyne can be used when the monomer ofFormula (E-9) is used as a polymerizable group, a polymerizable monomerhaving vinyl can be used when the monomer of Formula (E-10) is used as apolymerizable group, and a polymerizable monomer having thiol can beused when the monomer of Formula (E-11) is used as a polymerizablegroup.

In the above Formulas (E-12) and (E-13), symbol X denotes amide or esterbut may not be included. R₁ in the above Formulas (E-12) and (E-13) isthe same as R₁ of the above substructure that inhibits aggregation.

The substituent group represented by the above Formula (E-12) is aradical polymerization monomer and, specifically, may bealkyl(meth)acrylamides such as methyl(meth)acrylamide,ethyl(meth)acrylamide, n-propyl(meth)acrylamide,2-propyl(meth)acrylamide, n-butyl(meth)acrylamide,1-methylpropyl(meth)acrylamide, 2-methylpropyl(meth)acrylamide,tert-butyl(meth)acrylamide, n-pentyl(meth)acrylamide,1-methylbutyl(meth)acrylamide, 1-ethylpropyl(meth)acrylamide,tert-pentyl(meth)acrylamide, 2-methylbutyl(meth)acrylamide,3-methylbutyl(meth)acrylamide, 2,2-dimethylpropyl(meth)acrylamide,n-hexyl(meth)acrylamide, or the like; alkyl(meth)acrylates such asmethyl(meth)acrylate, ethyl(meth)acrylate, n-propyl(meth)acrylate,2-propyl(meth)acrylate, n-butyl(meth)acrylate,1-methylpropyl(meth)acrylate, 2-methylpropyl(meth)acrylate,tert-butyl(meth)acrylate, n-pentyl(meth)acrylate,1-methylbutyl(meth)acrylate, 1-ethylpropyl(meth)acrylate,tert-pentyl(meth)acrylate, 2-methylbutyl(meth)acrylate,3-methylbutyl(meth)acrylate, 2,2-dimethyl propyl(meth)acrylate,n-hexyl(meth)acrylate, 1-methylpentyl(meth)acrylate,1-ethylbutyl(meth)acrylate, 2-methylpentyl(meth)acrylate,3-methylpentyl(meth)acrylate, 4-methylpentyl(meth)acrylate,2-methylpentane-3-yl(meth)acrylate, 3,3-dimethylbutyl(meth)acrylate,2,2-dimethylbutyl(meth)acrylate, 1,1-dimethylbutyl(meth)acrylate,1,2-dimethylbutyl(meth)acrylate, 1,3-dimethylbutyl(meth)acrylate,2,3-dimethylbutyl(meth)acrylate, 1-ethylbutyl(meth)acrylate,2-ethylbutyl(meth)acrylate, heptyl(meth)acrylate, or the like;cyclopentene or cyclohexene such as propylene, 2-methyl-1-propylene,1-butene, 2-methyl-1-butene, 3-methyl-1-butene, 3,3-dimethyl-1-butene,3-methyl-2-ethyl-1-butene, 2,3-dimethyl-1-butene,2-tert-butyl-3,3-dimethyl-1-butene, 1-pentene, 2-methyl-1-pentene,3-methyl-1-pentene, 4-methyl-1-pentene, 2-methyl-3-ethyl-1-pentene,2,4,4-trimethyl-1-pentene, 1-hexene, or the like; vinylaryls such asvinylbenzene(styrene), 1-vinylindene, 5-vinylindene, 1-vinylpentarene,1-vinylnaphthalene, 2-vinylnaphthalene, 2-vinylazulene,9-vinyl-9H-fluorene, 2-vinyl-9H-fluorene, 1-vinylphenanthrene,2-vinylphenanthrene, 3-vinylphenanthrene, 6-vinylphenanthrene,8-vinylphenanthrene, 1-vinylanthracene, 2-vinylanthracene,9-vinylanthracene, 1-vinylacenaphthylene, 2-vinylbiphenylene,1-vinylnaphthacene, 2-vinylnaphthacene, 1-vinylpyrene, 4-vinylpyrene, orthe like; or the like.

The substituent group represented by the above Formula (E-13) may be ametathesis ring-opening polymerization monomer and, specifically, may benorbornene, acetyl norbornene, 5-methyl norbornene, 5-ethyl norbornene,5-butyl norbornene, 5-phenyl norbornene, 5-benzyl norbornene, 5-acetylnorbornene, 5-acetyloxy norbornene, 5-methoxycarbonyl norbornene,5-ethoxycarbonyl norbornene, 5-methyl-5-methoxycarbonyl norbornene, orthe like.

Each substituent group represented by the above Formulas (E-14) to(E-18) is a bifunctional monomer. The monomer represented by the aboveFormula (E-14) may be methyl diol, ethyl diol, propyl diol, butyl diol,pentyl diol, hexyl diol, cyclopropyl diol, phenyl diol, or the like. Themonomer represented by the above Formula (E-15) may be methyldicarboxylic acid, ethyl dicarboxylic acid, propyl dicarboxylic acid,butyl dicarboxylic acid, pentyl dicarboxylic acid, hexyl dicarboxylicacid, cyclopropyl dicarboxylic acid, phenyl dicarboxylic acid, or thelike. The monomer represented by the above Formula (E-16) may be methyldiamine, ethyl diamine, propyl diamine, butyl diamine, pentyl diamine,hexyl diamine, cyclopropyl diamine, phenyl diamine, or the like. Themonomer represented by the above Formula (E-17) may be methyldiisocyanate, ethyl diisocyanate, propyl diisocyanate, butyldiisocyanate, pentyl diisocyanate, hexyl diisocyanate, cyclopropyldiisocyanate, phenyl diisocyanate, or the like. The monomer representedby the above Formula (E-18) may be methyl diisothiocyanate, ethyldiisothiocyanate, propyl diisothiocyanate, butyl diisothiocyanate,pentyl diisothiocyanate, hexyl diisothiocyanate, cyclopropyldiisothiocyanate, phenyl diisothiocyanate, or the like. In the samemanner as the case of click reaction, also when a bifunctional monomeris used, a polymerizable monomer that can react with the bifunctionalmonomer can be suitably selected as a polymerizable monomer used forpolymer chain. For example, when the polymerizable group containsdicarboxylic acid, a polymerizable monomer containing diamine or diolcan be selected.

The compound represented by the above general Formula (1) may be thefollowing compounds, for example. Note that the following examples areprovided for better understanding and are not intended to limit thecompound represented by general Formula (1).

The compound (FLAP) represented by general Formula (1) can besynthesized by performing a coupling reaction using a palladium (Pd)catalyst or the like, for example, on a precursor represented by Formula(6) and a π-conjugated compound.

In the above general Formula (6), A, Y¹ to Y³, a1, a2, b, m, and n arethe same as those of general Formula (1).

Q1 to Q4 are halogen atoms or amino groups.

The mechanochromic light-emitting materials represented by Formulas (P1)and (P2) disclosed in Patent Literature 3 described above aresynthesized by performing an acene elongation reaction on the compoundsrepresented by the following Formulas (P3) and (P4).

In the above Formula (P3), n denotes an integer of 0 to 3. In the aboveFormula (P4), Y denotes a substituent group that inhibits aggregation ofmechanochromic light-emitting materials represented by Formulas (P1) or(P2), and Z denotes a polymerizable group. Specific examples of Y and Zare disclosed in Patent Literature 3 described above.

However, when the compound represented by Formula (P3) is used as astarting compound to synthesize mechanochromic light-emitting material,there is a problem of limited π-conjugated systems that can besynthesized because the aldehyde group of (P3) has carbon. On the otherhand, the embodiment disclosed in the present specification, by usingthe precursor represented by Formula (6), it is possible to introduce aπ-conjugated system to the positions of Q₁ to Q₄ of Formula (6) by acoupling reaction. Therefore, the absence of carbon of aldehydedisclosed in Patent Literature 3 provides wider options of π-conjugatedbased compounds to be coupled to a precursor. This enables introductionof a heterocyclic structure such as a perylene ring, and a compound(FLAP) having high spatial resolution is obtained. In addition, forexample, by performing a coupling reaction of a precursor with aπ-conjugated based compound whose π-conjugated based structure has beenslightly changed, it is also possible to synthesize a series compound(FLAP) having a different wavelength when the same stress is applied.Further, because of easy adjustment of the wavelength range for lightemission, it is possible to synthesize a FLAP or the like that emitlight of a wavelength out of the ultraviolet wavelength range that mayadversely affect living things, for example.

The coupling reaction may be the Suzuki-Miyaura coupling that causescoupling to a π-conjugate compound having organic boron by using a Pdcatalyst, the Negishi coupling that causes coupling to a π-conjugatecompound having organic zinc by using a Pd catalyst, the Stille couplingthat causes coupling to a π-conjugate compound having organic tin byusing a Pd catalyst, the Hiyama coupling that causes coupling to aπ-conjugate compound having organic silicon by using a Pd catalyst, theSonogashira coupling that causes coupling to a π-conjugate compoundhaving acetylene by using a Pd and Cu catalyst, the Buckwald-Hartwigcoupling that causes coupling to a π-conjugate compound having an aminogroup by using a Pd catalyst, the Kumada-Tamao coupling that causescoupling to a π-conjugate compound having organic magnesium by using aNi catalyst, a C—H aryl chemical reaction that causes coupling to aπ-conjugate compound having no functional group by using a transitionmetal catalyst such as Pd, and the like, and these schemes may be usedstepwise in combination.

An example of a synthesis procedure of a FLAP from the precursorrepresented by general Formula (6) will be described below.

The embodiment of a polymer compound includes a compound (FLAP) as apolymerizable component. FIG. 2A to FIG. 4B illustrate examples of theembodiment of the polymer compound. FIG. 2A illustrates an exampleincluding a FLAP as a main chain of a polymer. The embodimentillustrated in FIG. 2A is obtained by using a FLAP in which onemonofunctional polymerizable group is introduced to each of bothterminals (two polymerizable groups in total), as illustrated in FIG.2B. In the embodiment illustrated in FIG. 2A and FIG. 2B, thepolymerizable group illustrated as an example in E-1 to E-11 can be usedas a polymerizable group. Note that FIG. 2B illustrates an example fordescribing the position of the polymerizable group, and other compounds(FLAP) may be used. The same applies for FIG. 3B and FIG. 4B describedlater.

FIG. 3A illustrates an example including a FLAP as a cross-linkage pointof a polymer. The embodiment illustrated in FIG. 3A is obtained by usinga FLAP in which one bifunctional polymerizable groups is introduced toeach of both terminals (four polymerizable groups in total), asillustrated in FIG. 3B. In the embodiment illustrated in FIG. 3A andFIG. 3B, the polymerizable group illustrated as an example in E-12 toE-18 can be used as a polymerizable group.

FIG. 4A illustrates another example including a FLAP as a cross-linkagepoint of a polymer. The embodiment illustrated in FIG. 4A is obtained byusing a FLAP in which two monofunctional polymerizable groups areintroduced to each of both arms (four polymerizable groups in total), asillustrated in FIG. 4B. In the embodiment illustrated in FIG. 4A andFIG. 4B, the polymerizable group illustrated as an example in E-1 toE-11 can be used as a polymerizable group.

The polymer compounds illustrated in FIG. 2A to FIG. 4A can besynthesized by mixing the FLAP illustrated in FIG. 2B to FIG. 4B, apolymerizable monomer, and a catalyst or an initiator in an organicsolvent.

The polymerizable monomer forming the main chain of the polymer compoundcan include the FLAP illustrated in FIG. 2B to FIG. 4B and is notparticularly limited as long as the FLAP can cause a conformation changewhen stress is applied to the main chain. For example, the polymerizablemonomer may be a monomer that can cause sequential polymerization suchas polyaddition or polycondensation, radical polymerization,ring-opening polymerization, or click reaction.

The monomer that can cause polyaddition (for example, polyurethanesynthesis) and polycondensation may be a monomer containing thepolymerizable group illustrated in the above Formulas (E-1) to (E-7) asexamples. Further, as the monomer that can cause click reaction, apolymerizable monomer having azide can be used when the monomer ofFormula (E-8) is used as the polymerizable groups (E¹ to E³) of the FLAPdescribed in general Formula (1), as described above. Similarly, apolymerizable monomer having alkyne can be used when the monomer ofFormula (E-9) is used as the polymerizable groups (E¹ to E³), apolymerizable monomer having vinyl can be used when the monomer ofFormula (E-10) is used as the polymerizable groups (E¹ to E³), and apolymerizable monomer having thiol can be used when the monomer ofFormula (E-11) is used as the polymerizable groups (E¹ to E³).

The monomer that can cause ring-opening polymerization may benorbornene, acetyl norbornene, ethylene oxide, propylene oxide,ethyleneimine, trimethylene oxide, tetrahydrofuran, β-propiolactone,γ-butyrolactone, ε-caprolactone, or the like.

The monomer that can cause radical polymerization may be an ethylene; avinyl aromatic monomer, for example, styrene, α-methylstyrene,o-chlorostyrene or vinyl toluene; an ester of vinyl alcohol andmonocarboxylic acid having 1-18 carbon atoms, for example, vinylacetate, vinyl propionate, vinyl-n-butyrate, vinyl laurate, and vinylstearate; advantageously, an ester of α,β-monoethylene unsaturatedmonocarboxylic or dicarboxylic acid having 3-6 carbon atoms(particularly, acrylic acid, methacrylic acid, maleic acid, fumaricacid, and itaconic acid) and alkanol having generally 1-12,advantageously 1-8, and particularly 1-4 carbon atoms, for example,particularly, methyl acrylate, methyl methacrylate, ethyl acrylate,ethyl methacrylate, n-butyl acrylate, n-butyl methacrylate, isobutylacrylate, isobutyl methacrylate, 2-ethylhexyl acrylate, 2-ethylhexylmethacrylate, dimethyl maleate, di-n-butyl maleate, nitrile ofα,β-monoethylene unsaturated carboxylic acid such as acrylonitrile, anda C4-C8 conjugated diene such as 1,3-butadiene and isoprene; or thelike.

In synthesis, the above monomer may be used alone, or two or more typesof monomers may be used to form a random copolymer.

The catalyst or the initiator is not particularly limited as long as apolymer compound can be synthesized from a polymerizable monomer and acompound (FLAP). For example, the catalyst may be Grubb's catalyst,Hoveyda-Grubb's catalyst, Ru complex, tungsten chloride, tetramethyltin,or the like. Further, the initiator may be azobis isobutyronitrile,benzoyl peroxide, di-tert-butyl peroxide, hydrogen peroxide-iron(II)salt, persulphate-sodium hydrogen sulfite, triethyl borane, or the like.

With respect to the main chain, the above polymerizable monomer can besuitably selected so as to have a desired resin characteristic. Forexample, when a hard polymer (high Tg, high yield stress, smallelongation) is intended to be synthesized, a polymerizable monomer whosemain chain is polystyrene, polymethyl methacrylate, or the like can beused. Further, when a soft polymer (low Tg, low yield stress, largeelongation) is intended to be synthesized, a polymerizable monomer whosemain chain is polyurethane, polybutadiene, polyacetyl norbornene,polydimethylsiloxane, or the like can be used.

The compound illustrated in the embodiment can be used for a viscosityprobe by using the same method as illustrated in Patent Literature 2,for example.

While the present invention will be specifically described below withexamples, these examples are solely provided for reference of specificaspects. These examples are neither to limit the scope of the inventiondisclosed by this application nor to imply such limitation.

EXAMPLES

In the following examples, purchased reagents were used without changeunless otherwise specified.

Wakogel, C-300 or C-400 (by Wako Pure Chemical Co.) was used for silicagel column chromatography.

¹H and ¹³C NMR spectrum measurement was used for structuraldetermination of a resultant compound.

(¹H and ¹³C NMR spectrum measurement)

Equipment: ECA-600 by JOEL Ltd.

Measured frequency: 600 MHz at ¹H-NMR measurement, 151 MHz at ¹³C-NMRmeasurementInternal reference: CDCl₃

Molecular weights were measured by mass spectrometry based onhigh-resolution atmospheric pressure chemical ionization (APCI).

(Mass Spectrometry)

Equipment: micro TOF Time-of-flight mass spectrometer by BRUKER

Further, various optical analysis was performed under the followingconditions.

(Ultraviolet and Visible Absorption Spectrum Measurement) Equipment:Shimadzu, UV-3600 and UV-2550 by Shimadzu Corporation (Ultraviolet andVisible Fluorescence Spectrum Measurement) Equipment: Shimadzu, RF5300PCby Shimadzu Corporation (Absolute Fluorescence Quantum YieldMeasurement) Equipment: HAMAMATSU, C9920-02S by Hamamatsu Photonics K.K. (Single-Molecule Fluorescence Imaging)

Equipment: inverted microscope IX71 by Olympus Corporation, imagingspectrometer for microscope Connection CLP-50 by Bunkoukeiki Co., Ltd.,and electron multiplying CCD camera iXon by Andor Technology, Inc. (usedin combination of three items)

[Synthesis 1 of Precursor]

A compound (b) was synthesized along the following synthesis route.

Synthesis of 1,2-bis(dibromomethyl)-4,5-dichlorobenzene (Compound (a))

1,2-bis(bromomethyl)-4,5-dichlorobenzene (synthesized in accordance witha method described in Synthetic communication, 1983, 13, p 639-648, 5.0g, 15 mmol), N-bromosuccinimide (8.0 g, 45 mmol), and azobisisobutyronitrile (20 mg, 0.08 mmol) were dissolved in benzotrifluoride(100 mL) in a UV irradiation reaction vessel. This solution was stirredunder UV irradiation by using a high-pressure mercury lamp at 100degrees Celsius for 7 hours under N₂ atmosphere. Subsequently, afterthis solution was cooled to room temperature, the mixture was filteredto distill the solvent. After purification by column chromatographyusing hexane, a compound (a) was obtained as a white solid (3.9 g, yield53%). The spectrum data of the compound (a) was as follows.

-   -   ¹H NMR (CDCl₃, 600 MHz): δ 7.78 (br, 2H) 6.99 (br, 2H); ¹³C NMR        (CDCl₃, 150 MHz): δ137.32 (br), 134.78, 131.45 (br), 33.96;        APCI-HRMS: m/z 406.7249 ([M-Br]⁺, C₈H₄Br₃Cl₂ requires:        406.7235).

Synthesis of 2,3,8,9-tetrachlorodibenzo[a,e]cyclooctatetraene (Compound(b))

1,2-bis(dibromomethyl)-4,5-dichlorobenzene (0.85 g, 1.7 mmol) and NaI(1.6 g, 10 mmol) were dissolved in anhydrous dimethylformamide (10 mL).This solution was heated and refluxed and then stirred for 4.5 hoursunder N₂ atmosphere. Subsequently, after this solution was cooled toroom temperature, a compound (b) was obtained as a white solid (64 mg,yield 22%) by column chromatography using hexane. The spectrum data ofthe compound (b) was as follows.

-   -   ¹H NMR (CDCl₃/C₆D₆(1%), 600 MHz): δ 7.18 (s, 4H); ¹³C NMR        (CDCl₃/C₆D₆(1%), 150 MHz): δ136.53, 132.60, 131.53, 130.70;        APCI-HRMS: m/z 399.9375 ([M]⁺, C₁₆H₈Cl₄ requires: 339.9380).

Synthesis 2 of Precursor

A compound (f) was synthesized along the following synthesis route.

Synthesis of 1,2-bis(trimethylsilylpropyl)-4,5-dichlorobenzene (Compound(c))

All the procedures described below were performed under N₂ atmosphere.

Trimethylsilylacetylene (15 mL, 110 mmol) was dissolved in THF (60 mL),which was cooled in an ice water bath. Next, a tetrahydrofuran (THF)solution of isopropyl magnesium chloride (2 M, 54 mL, 110 mmol) wasslowly added to the above solution, and after completion of theaddition, the mixture was stirred at room temperature for 1 hour. Copperbromide (I) (2.8 g, 19 mmol) was then added, and this mixture wasstirred for another 30 minutes. Furthermore,1,2-bis(bromomethyl)-4,5-dichlorobenzene (7.1 g, 21 mmol) was added, andthe mixture was heated and refluxed for 4.5 hours. Then, after cooled toroom temperature, the mixture was poured into a saturated ammoniumchloride aqueous solution (800 mL), and the product was extracted withhexane. A compound (c) was obtained as white powder (4.3 g, yield 55%)by column chromatography (hexane/ethyl acetate, 100/0.5, v/v). Thespectrum data of the compound (c) was as follows.

-   -   ¹H NMR (CDCl₃, 600 MHz): δ 7.54 (s, 2H) 3.56 (s, 4H); 0.19 (s,        18H); ¹³C NMR (CDCl₃, 150 MHz): δ134.49, 131.08, 130.66, 102.02,        88.84, 23.44, 0.12; APCI-HRMS: m/z 367.0883 ([M+H]⁺,        C₁₈H₂₅Cl₂Si₂ requires: 367.0866).

Synthesis of 1,2-dipropynyl-4,5-dichlorobenzene (Compound (d))

1,2-bis(trimethylsilylpropynyl)-4,5-dichlorobenzene (210 mg, 0.57 mmol)synthesized as described above and silver nitrate (0.97 g, 5.7 mmol)were added to a mixture solution of dichloromethane (10 mL), water (1.4mL), and acetone (1 mL). This mixture solution was vigorously stirred atroom temperature for 1 hour, and 35 mass % of concentrated hydrochloricacid was gently added to the suspension. This mixture was stirred foranother 1 hour and filtered. The organic phase was washed with asaturated saline solution, passed through an anhydrous sodium sulfatepad, and then passed through a celite pad. A compound (d) was obtainedas a colorless solid (128 mg, yield 100%). The spectrum data of thecompound (d) was as follows.

-   -   ¹H NMR (CDCl₃, 600 MHz): δ 7.57 (s, 2H) 3.55 (d, J=2.8 Hz, 4H);        2.25 (t, J=2.8 Hz, 2H): ¹³C NMR (CDCl₃, 150 MHz): δ134.14,        131.38, 130.65, 79.82, 72.21, 22.07; APCI-HRMS: m/z 223.0069        ([M+H]⁺, C₁₂H₈Cl₂ requires: 223.0076).

Synthesis of Compound (e)

Next, the compound (d) (130 mg, 0.57 mmol) synthesized by the methoddescribed above, NiBr₂ (DME) (43 mg, 0.14 mmol), activated zinc powder(17 mg, 0.28 mmol), and water (2.4 μL, 0.14 mmol) were dissolved in THF(2.5 mL) in a Schlenk. The above mixture was frozen and deaired, theSchlenk was then sealed under N₂ atmosphere, and the mixture was heatedat 60 degrees Celsius for 1 hour while being stirred. The mixture wasthen cooled to room temperature and filtered with celite. The solventwas distilled, and a compound (e) was obtained as light yellow powder(120 mg, yield 94%). The spectrum data of the compound (e) was asfollows.

-   -   ¹H NMR (CDCl₃, 600 MHz): δ 7.20 (s, br, 4H), 5.83 (s, br, 4H),        3.25 (s, br, 8H); ¹³C NMR (CDCl₃, 150 MHz): δ 134.30, 133.01,        131.50, 129.76, 129.46, 34.36; APCI-HRMS: m/z 445.0088 ([M+H]⁺,        C₂₄H₁₇Cl₄ requires: 445.0079).

Synthesis of Compound (f)

The compound (e) (120 mg, 0.27 mmol) obtained by the method describedabove and 2,3-Dichloro-5,6-dicyano-1,4-benzoquinone (Tokyo ChemicalIndustry Co., Ltd., 134 mg, 0.59 mmol) were dissolved in toluene (3.5mL), which was stirred at room temperature for 1 hour. The obtainedmixture was filtered, silica gel was added to the filtrate to distillthe solvent, and thereby the residue was adsorbed in the silica gel. Thesilica gel to which a compound (f) was absorbed was used to performpurification by silica gel column chromatography (hexane and thendichloromethane), and the compound (f) was obtained as white powder (26mg, yield 22%). The spectrum data of the compound (f) was as follows.

-   -   ¹H NMR (CDCl₃, 600 MHz): δ 7.79 (s, 4H), 7.48, (s, 4H), 7.03 (s,        4H); ¹³C NMR (CDCl₃, 150 MHz): δ 136.10, 133.24, 131.30, 130.47,        128.47, 126.94: APCI-HRMS: m/z 440.9763 ([M+H]⁺, C₂₄H₁₃Cl₄        requires: 440.9766).

Synthesis 1 of FLAP Precursor

A mixture of9-(4,4,5,5-tetramethyl-1,3,2-dioxaborolanyl)-N-(2,6-diisopropylphenyl)-1,6-bis(4-tert-butylphenoxy)perylene-3,4-dicarboxymide(compound (g); synthesized by a method described in New Journal ofChemistry, 2016, 40, p 8032-8052, 200 mg, 0.22 mmol), the compound (b)synthesized in the section of [Synthesis 1 of precursor] (34 mg, 0.10mmol), palladium(II) acetate (Pd(OAc)₂) (2.3 mg, 10 μmol),2-cyclohexylphosphino-2′,4′,6′-triisopropyl biphenyl (XPhos; 9.5 mg, 20μmol), tripotassium phosphate (K₃PO₄; 110 mg, 0.50 mmol), and water (30μL) was dissolved in THF (5 mL) in a Schlenk.

The obtained mixture was frozen and deaired, the Schlenk was then sealedunder N₂ atmosphere, and the mixture was heated at 60 degrees Celsiusovernight while being stirred. The mixture was then cooled to roomtemperature, the solvent was evaporated, and an isomeric mixture (h) wasobtained as a red solid (62 mg, yield 34%) by column chromatography(hexane/dichloromethane, 1/1, v/v). The spectrum data of the above (h)was as follows.

-   -   ¹H NMR (CDCl₃, 600 MHz): δ 9.38-9.36 (m, 4H), 8.33-8.32 (m, 4H),        7.58-7.46 (m, 4H), 7.46-7.39 (m, 11H), 7.34 (s, 1H), 7.30-7.28        (m, 5H), 7.16 (s, 1H), 7.12-7.07 (m, 11H), 6.88 (d, J=5.0 Hz,        1H), 6.80 (d, J=2.8 Hz, 1H), 6.74 (d, J=5.0 Hz, 1H), 2.73-2.71        (m, 4H), 1.34-1.33 (m, 36H), 1.15-1.13 (m, 24H).

Next, the above isomeric mixture (h) (45 mg, 0.025 mmol) andPdCl₂(PCy₃)₂ (6.0 mg, 8.1 μmol) were dried in vacuum in a Schlenk.1,8-diazabicyclo[5.4.0]undeca-7-ene (25 μL, 0.17 mmol) anddimethylacetamide (2.5 mL) were added to this and mixed. The obtainedmixture was frozen and deaired, the Schlenk was then sealed under N₂atmosphere, and the mixture was heated at 140 degrees Celsius for 24hours while being stirred. The mixture was then cooled to roomtemperature and separated by using silica gel column chromatography(hexane/dichloromethane, 1/2, v/v), and a compound (i) was obtained as aviolet solid (13 mg, yield 30%). The spectrum data of the compound (i)was as follows.

-   -   ¹H NMR (CDCl₃/C₆D₆(1%), 600 MHz): δ 9.48 (d, J=8.3 Hz, 4H), 8.38        (s, 4H), 7.93 (d, J=8.3 Hz, 4H), 7.67 (s, 4H), 7.48-7.46 (m,        10H), 7.32 (d, J=7.8 Hz, 4H), 7.17-7.15 (m, 8H), 7.01 (s, 4H),        2.79-2.75 (m, 4H), 1.39 (s, 36H), 1.18 (d, J=6.9 Hz, 24H); ¹³C        NMR (CDCl₃/C₆D₆(1%), 150 MHz): δ 163.33, 155.15, 153.09, 147.65,        145.77, 138.10, 137.50, 137.02, 134.00, 129.78, 129.56, 128.38,        127.38, 126.81, 126.23, 124.05, 123.85, 122.80, 122.32, 121.55,        118.95, 34.60, 31.6, 29.23, 24.15. UV-vis-NIR (toluene):        λ_(max)(ε) 319 (9.1×10⁴) 522 (8.9×10⁴), 566 (1.3×10⁵).

Synthesis 2 of FLAP Precursor

A mixture of the compound (g) synthesized in the section of [Synthesis 1of FLAP precursor] (45 mg, 50 μmol), the compound (f) synthesized in thesection of [Synthesis 2 of precursor] (8.8 mg, 20 μmol), palladium(II)acetate (Pd(OAc)₂) (0.45 mg, 2.0 μmol),2-dicyclohexylphosphino-2′,4′,6′-triisopropyl biphenyl (XPhos; 1.9 mg,4.0 μmol), tripotassium phosphate (21 mg, 0.10 mmol), and water (20 μL)was dissolved in THF (1.5 mL) in a Schlenk. The obtained mixture wasfrozen and deaired, the Schlenk was then sealed under N₂ atmosphere, andthe mixture was heated at 60 degrees Celsius overnight while beingstirred. The mixture was then cooled to room temperature, the solventwas evaporated. Purification was performed by column chromatography(hexane/dichloromethane, 1/1, v/v), and an isomeric mixture (j) wasobtained as a red solid (16 mg, yield 42%). The spectrum data of theabove (j) was as follows.

-   -   ¹H NMR (CDCl₃, 600 MHz): δ 9.42-9.40 (m, 2H), 9.36-9.34 (m, 2H),        8.34-8.33 (m, 4H), 7.91 (d, J=11 Hz, 2H), 7.45 (d, J=11 Hz, 2H),        7.66-7.60 (m, 4H), 7.54-7.49 (m, 4H), 7.47-7.40 (m, 12H),        7.30-7.29 (m, 4H), 7.16-7.06 (m, 12H), 2.74-2.72 (m, 4H),        1.34-1.33 (m, 36H), 1.16-1.15 (m, 24H), ESI-HRMS: m/z 1923.7869        ([M+H]⁺, C₁₃₂H₁₁₃Cl₂N₂O₈ requires: 1923.7869).

The above isomeric mixture (j) (30 mg, 0.016 mmol) and PdCl₂ (4.0 mg,5.4 μmol) were dried in vacuum in a Schlenk. A mixture was made byadding 1,8-diazabicyclo[5.4.0]undeca-7-ene (15 μL, 0.10 mmol) anddimethylacetamide (2.5 mL) thereto. The obtained mixture was frozen anddeaired, the Schlenk was then sealed under N₂ atmosphere, and themixture was heated at 140 degrees Celsius for 22 hours while beingstirred. The mixture was then cooled to room temperature and separatedby using column chromatography (hexane/dichloromethane, 1/2, v/v). Withprecipitation of a benzene/methanol co-solvent system, a compound (k)was obtained as a dark blue solid (9.0 mg, 30%). The spectrum data ofthe compound (k) was as follows. The fluorescent wavelength of thecompound (k) in a toluene solution was 603 nm, and the fluorescentquantum yield was 72%.

-   -   ¹H NMR (CDCl₃/C₆D₆(1%), 600 MHz): δ 9.54 (d, J=7.8 Hz, 4H), 8.42        (s, 4H), 8.17 (s, 4H), 8.03 (d, J=7.8 Hz, 4H), 7.74 (s, 4H),        7.50-7.47 (m, 10H), 7.35 (d, J=7.8 Hz, 4H), 7.16-7.15 (m, 12H):        ¹³C NMR (CDCl₃/C₆D₆(1%), 150 MHz): δ163.34, 154.66, 153.21,        147351, 145.78, 137.91, 137.37, 135.58, 134.98, 133.48, 132.57,        131.57, 130.84, 130.18, 129.56, 129.36, 127.36, 126.69, 124.19,        124.04, 123.76, 122.76, 122.10, 120.86, 120.80, 118.72, 34.58,        31.60, 29.24, 24.16; ESI-HRMS: m/z 1851.8486 ([M+H]⁺,        C₁₃₂H₁₁₁N₂O₈ requires: 1851.8335); UV-vis-NIR (toluene:        λ_(max)(ε) 338 (7.3×10⁴), 503 (2.7×10⁴), 542 (7.8×10⁴), 590        (1.3×10⁵).

Synthesis 3 of FLAP Precursor

The compound (I) (synthesized in accordance with a method described inChemistry of Materials, 2014, 26, p 4433-4446, 73 mg, 0.16 mmol), thecompound (f) synthesized in the section of [Synthesis 2 of precursor](28 mg, 63 μmol), Pd(OAc)₂ (1.5 mg, 6.6 μmol), XPhos (6.0 mg, 21 μmol),K₃PO₄ (67 mg, 0.32 mmol), and H₂O (10 μL) were dissolved in THF (2.5 mL)in a Schlenk. After the same operation as that in the synthesis methodof the compound (j) in the section of [Synthesis 2 of FLAP precursor],the mixture was heated at 60 degrees Celsius for 12 hours. Then, afterseparation by silica gel column chromatography using methylene chlorideas a solvent, the Suzuki coupling product was obtained as a mixture.

The obtained mixture was mixed to PdCl₂ (9.0 mg, 12 μmol) and dried invacuum in a Schlenk. Furthermore, 1,8-diazabicyclo[5.4.0]undeca-7-ene(45 μL, 0.32 mmol), and dimethylacetamide (2.1 mL) were added, and afterthe same operation as the synthesis method of the compound (k) in thesection of [Synthesis 2 of FLAP precursor], the mixture was heated at140 degrees Celsius for 24 hours to cause reaction. The mixture wascooled to room temperature and separated by using column chromatography(hexane/dichloromethane, 1/4, v/v). By precipitation with adichloromethane/methanol co-solvent system, a compound (m) was obtainedas an orange solid (20 mg, yield 31%). The spectrum data of the compound(m) was as follows. The fluorescent wavelength in a toluene solution ofthe compound (m) was 497 nm, and the fluorescent quantum yield was 52%.

-   -   ¹H NMR (CDCl₃, 600 MHz): δ 8.57 (d, J=7.2 Hz, 4H), 8.19 (s, 4H),        8.05 (d, J=7.2 Hz, 4H), 7.72 (s, 4H), 7.46 (t, J=7.8 Hz, 2H),        7.32 (d, J=7.8 Hz, 4H), 7.14 (s, 4H), 2.79-2.76 (m, 4H), 1.15        (d, J=6.4 Hz, 24H); ¹³C NMR (CDCl₃, 150 MHz): δ 164.11, 145.95,        142.75, 137.55, 136.65, 134.52, 133.52, 133.30, 132.97, 131.30,        129.67, 129.55, 126.67, 124.09, 122.93, 121.84, 120.06, 29.24,        24.13; APCI-HRMS: m/z 1010.4168 ([M]; C₇₂H₅₄N₂O₄ requires:        1010.4078); UV-vis-NIR (toluene): λ_(max) (ε) 343 (1.1×10⁵), 447        (6.3×10⁴), 477 (8.2×10⁴).

Synthesis 4 of FLAP Precursor

Synthesis of Oxepine FLAP (Compound (q))

2-Hydroxy-3-naphthaldehyde (synthesized in accordance with a methoddescribed in Journal of Organic Chemistry, 1988, 53, p 5345-5348, 90 mg,0.50 mmol) and potassium carbonate (0.14 g, 1.0 mmol) were dissolved inacetonitrile (2 mL), which was cooled in an ice bath. An acetonitrile (2mL) solution of tosylchloride (0.12 g, 0.60 mmol) was added to thissolution. Next, the ice bath was removed, and this solution was stirredat room temperature for 2 hours. Water was added for quenching reaction,and the product was then extracted with ethyl acetate. The organic layerwas passed through anhydrous sodium sulfate and silica gel column, and acompound (n) was obtained as a crude product.

Next, 2-bromobenzyl triphenylphosphonium bromide (synthesized inaccordance with a method described in Organic Letters, 2013, 15, p5448-5451, 0.31 g, 0.6 mmol) is suspended in anhydrous THF, which wascooled in an ice bath. Potassium t-butoxide (t-BuOK: 80 mg, 0.71 mmol)was added to the solution in the ice bath, and the mixture was stirredat 0 degree Celsius for 30 minutes under a nitrogen atmosphere. Thecompound (n) that was a crude product was then dissolved in THF (5 mL)and added to a reaction mixture in the ice bath, and the mixture wasstirred for 12 hours while the reaction temperature was graduallyincreased back to room temperature. Water (25 mL) and ethyl acetate (50mL) were added to extract a product, and the organic layer was passedthrough anhydrous sodium sulfate and silica gel column. The solvent wasdistilled, and a compound (o) was obtained as a crude product.

The compound (o) was dissolved in ethanol (15 mL) and water (15 mL),potassium hydroxide (0.9 g, 16 mmol) was added, and the reaction productwere heated and refluxed for 1 hour and then cooled back to roomtemperature. Next, 10 mass % of hydrochloric acid was used to adjust pHto 4, and extraction was performed with dichloromethane. The organiclayer was washed with a sodium hydrogen carbonate solution, and theorganic layer was passed through anhydrous sodium sulfate and silica gelcolumn. The solvent was then distilled, and a compound (p) was obtainedas a crude product.

The crude product (p) was mixed with potassium carbonate (0.28 g, 2.0mmol) and dissolved in NMP (6 mL), and the mixture was heated at 120degrees Celsius for 20 hours under a nitrogen atmosphere. The reactionproduct was subjected to silica gel column chromatography(hexane/dichloromethane, 3/1 by volume), and a compound (q) was obtainedas a colorless solid (69 mg, 57%). The spectrum data of the compound (q)was as follows. The fluorescent wavelength in a dichloromethane solutionof the compound (q) was 476 nm, and the fluorescent quantum yield was10%.

-   -   ¹H (CDCl₃, 600 MHz): δ 7.77-7.75 (m, 2H), 7.62 (s, 1H), 7.60 (s,        1H), 7.44-7.38 (m, 2H), 7.32-7.28 (m, 2H), 7.21-7.18 (m, 1H),        7.14-7.11 (m, 1), 6.87 (d, J=12 Hz, 1H), 6.70 (d, J=12 Hz, 1H);        ¹³C NMR (CDCl₃, 150 MHz): δ 157.60, 156.38, 134.51, 131.24,        130.74, 130.51, 130.18, 129.87, 129.77, 128.89, 127.90, 127.20,        126.62, 125.65, 125.05, 121.67, 117.96.

Synthesis 5 of FLAP Precursor

Synthesis of Compound (r)

2-bromo-3-bromomethylnaphthalene (synthesized in accordance with amethod described in Angewandte Chemistry International Edition, 2016,55, p 11120-11123, 60 mg, 0.20 mmol) and triphenylphosphine (PPh₃, 60mg, 0.23 mmol) were dissolved in dehydrated dimethylformamide (2 mL),which was stirred at room temperature for 12 hours under a nitrogenatmosphere. Methylene chloride (2 mL) and diethyl ether (40 mL) werethen added, and a product was precipitated. The suspension was filtered,washed with diethyl ether, and thereby a compound (r) was obtained as awhite solid (87 mg, yield 80%). The spectrum data of the compound (r)was as follows.

-   -   ¹H NMR (CDCl₃, 600 MHz) δ 8.09 (d, J=3.7 Hz, 1H), 7.89 (s, 1H),        7.80-7.71 (m, 9H), 7.67-7.60 (m, 8H), 7.50-7.43 (m, 2H), 5.88        (d, J=14 Hz, 2H); ¹³C NMR (CDCl₃, 150 MHz): δ 135.25, 134.40,        134.33, 133.81, 132.94, 132.89, 132.08, 131.57, 130.33, 130.24,        128.17, 127.82, 127.05, 126.55, 124.22, 124.15, 123.62, 117.64,        117.08, 31.09, 30.76; ³¹P NMR (CDCl₃, 243 MHz): δ 22.96.

Synthesis of Oxepine FLAP (Compound (u))

The above compound (r) (87 mg, 0.16 mmol) was suspended in anhydrous THF(2.5 mL), which was cooled in an ice bath. To the solution in the icebath, t-BuOK (20 mg, 0.18 mmol) was added, and the mixture was stirredat 0 degree Celsius for 30 minutes under a nitrogen atmosphere. A crudeproduct of the compound (n) synthesized at 25 mol % of scale of themethod described in Example 6 was then dissolved in THF (1 mL) and addedto the reaction mixture in the ice bath, and the mixture was stirred for12 hours while the reaction temperature was gradually increased back toroom temperature. Water (7 mL) and ethyl acetate (15 mL) were added toextract a product, and the organic layer was passed through anhydroussodium sulfate and silica gel column. The solvent was distilled, and acompound (s) was obtained as a crude product.

The compound (s) was dissolved in ethanol (5 mL) and water (5 mL),potassium hydroxide (0.30 g, 5.3 mmol) was added, the reaction mixturewas refluxed for 1 hour, and the temperature was increased back to roomtemperature. This reaction liquid was subjected to the same operation asthat for the compound (p) of Example 6 below, and a compound (t) wasobtained as a crude product.

The crude product (t) was mixed with potassium carbonate (90 mg, 0.64mmol) and dissolved in NMP (2 mL), which was heated at 120 degreesCelsius for 20 hours under nitrogen. The reaction mixture was subjectedto silica gel column chromatography (hexane/dichloromethane, 4/1 byvolume), a compound (u) was obtained as an insoluble colorless solid(6.0 mg, yield 13%). The spectrum data of the compound (u) was asfollows. The fluorescent wavelength of the compound (u) in adichloromethane solution was 479 nm, and the fluorescent quantum yieldwas 5%.

-   -   ¹H NMR (DMSO-d₆, 120° C., 600 MHz): δ 7.88-7.85 (m, 6H), 7.79        (s, 2H), 7.49-7.45 (m, 4H), 6.98 (s, 2H); ¹³C NMR (DMSO-d₆, 120°        C., 150 MHz): δ 154.80, 133.38, 130.30, 129.54, 128.93, 128.52,        127.11, 126.34, 126.10, 125.05, 116.96.

Synthesis 6 of FLAP Precursor

Synthesis of Compound (v)

After α,α, α′,α′, 4,5-hexabromo-o-xylene (Tokyo Chemical Industry Co.,Ltd.) (1.21 g, 2.0 mmol) and sodium iodide (3.0 g, 20 mmol) were driedin vacuum for 10 minutes in a Schlenk, 3 mL of ultra-dehydrated DMF wasadded under an argon atmosphere, and the mixture was heated to 170degrees Celsius and stirred for 4 hours. This reaction mixture wasallowed to be cooled to room temperature, a sodium thiosulfate solutionwas added, and extraction was performed with hexane/dichloromethanemixture solvent (10:1 by volume). The organic layer was passed throughanhydrous sodium sulfate to remove water, the solvent was distilled, andthereby a dark brown solid of a crude product was obtained. Purificationby silica gel column chromatography (hexane/dichloromethane mixturesolvent, 30:1) was performed on the crude product, and a compound (v)was obtained as a white solid (158 mg, 30%). The spectrum data of thecompound (v) was as follows.

-   -   ¹H NMR (CDCl₃, 600 MHz): δ/ppm=7.31 (s, 4H), 6.65 (s, 4H); ¹³C        NMR (CDCl₃, 600 MHz): δ/ppm=137.32 (4C), 133.8141 (4C), 133.8141        (4C), 132.5693 (4C); MARDI-TOF-MS: m/z=519.73

Synthesis of Phenazine Based FLAP Precursor (Compound (W))

The compound (v) (156 mg, 0.30 mmol), 4,5-dihexyloxy-1,2-phenylenediamine (synthesized by a method described in J. Mater.Chem., 2012, 22, 4450, 196 mg, 0.64 mmol), palladium(II) acetate (14 mg,0.06 mmol), 2-dicyclohexylphosphino-2′,6′-dimethoxybiphenyl (SPhos; 25mg, 0.06 mmol), and cesium carbonate (650 mg, 6.6 mmol) were dried invacuum for 10 minutes in a Schlenk, toluene 2.4 mL deaired under anargon atmosphere was added, and the mixture was heated at 110 degreesCelsius for 32 hours. Palladium(II) acetate (14 mg, 0.06 mmol) and SPhos(25 mg, 0.06 mmol) were added, and the mixture was further heated at 110degrees Celsius for 16 hours. This reaction mixture was allowed to becooled to room temperature, diluted with excessive amount of chloroform,and suctioned and filtered, and the filtrate was condensed by using arotary evaporator to obtain a dark brown solid crude product. The crudeproduct was purified by silica gel column chromatography(dichloromethane/ethyl acetate mixture solvent, 5:1 by volume) and thengel filtration chromatography (chloroform, 0.5% triethylamine mixturesolvent), and a dark brown crude crystal was obtained. Recrystallizationwas performed using chloroform as a good solvent and methanol as a poorsolvent, a compound (w) was obtained as a yellow crystal (11 mg, 4%).The spectrum data of the compound (w) was as follows. The fluorescentwavelength in a dichloromethane solution of the compound (w) was 518 nm,and the fluorescent quantum yield was 42%. Further, in a polymer thinfilm, the fluorescent wavelength was 460 nm, and the fluorescent quantumyield was 13%. While long wavelength fluorescence due to the planarshape was exhibited in the dichloromethane solution, short wavelengthfluorescence due to the V-shape was exhibited in the polymer thin film.Since this indicates that the planar shape and the V-shape havedifferent π-conjugate structures, respectively, it is expected that thecompound (w) functions as a stress probe.

-   -   ¹H NMR (CDCl₃, 600 Hz): δ/ppm=7.92 (s, 4H), 7.24 (s, 4H), 7.23        (s, 4H), 7.30 (s, 4H), 4.18 (t, J=6.6 Hz, 8H), 1.92 (tt, J₁==6.7        Hz, J₂=6.7 Hz, 8H), 1.35-1.38 (m, 24H), 0.91 (t, J=7.0 Hz, 12H),        ¹³C NMR (CDCl₃, 600 MHz): δ/ppm=154.63 (4C, C), 142.49 (4C, CH),        140.86 (4C, C), 137.95 (4C, C), 133.27 (4C, CH), 123.38 (4C, C),        105.57 (4C, CH), 69.40 (4C, CH₂), 31.65 (4C, CH₂), 28.81 (4C,        CH₂), 25.82 (4C, CH₂) 22.73 (4C, CH₂), 14.15 (4C, CH₃).        MARDI-TOF-MS: m/z=808.71

Synthesis 7 of FLAP Precursor

Synthesis of Acetylene Modified FLAP Precursor

An isopropyl magnesium chloride solution (2.0 M, 11 mL oftetrahydrofuran, 22 mol) and tetrahydrofuran (20 mL) were put in aSchlenk, and triisopropylsilylacetylene (4.9 mL, 22 mmol) was drippedunder argon. The reaction mixture liquid was heated to 60 degreesCelsius and stirred for 20 minutes. After cooled back to roomtemperature, a cyclooctatetraene condensed-ring anthraquinone dimer(synthesized in accordance with a method described in ZhurnalOrganicheskoi Khimii (1977), 13(6), 1341) (0.84 g, 1.8 mmol) andtetrahydrofuran (5 mL) were added to the reaction mixture liquid, andthe suspension was stirred at 60 degrees Celsius for 35 hours. Aftercooled back to room temperature, tin (II) chloride (2.1 g, 11 mmol)dissolved in 10 mass % of dilute hydrochloric acid (10 mL) was added,and the mixture was stirred at 60 degrees Celsius for 2 hours. Thereaction liquid was diluted with methylene chloride and extracted. Afterthe organic layer was washed with a saturated saline solution anddehydrated with anhydrous sodium sulfate, the solvent was distilledaway. The residue was subjected to silica gel column chromatography(eluate: hexane and then hexane/dichloromethane mixture liquid, 20/1 byvolume), and a compound (x) was obtained as a yellow solid (250 mg,12%). Furthermore, recrystallization was performed with dichloromethaneand a methanol solvent, and thereby a product was able to be purified.The spectrum data of the product was as follows. The fluorescentwavelengths of the compound (x) in the dichloromethane solution were 470nm and 504 nm, and the fluorescent quantum yield was 18%. In thecrystal, the fluorescent wavelengths were 544 nm and 588 nm, and thefluorescent quantum yield was 10%. While short wavelength fluorescencedue to the V-shape was exhibited in the dichloromethane solution, longwavelength fluorescence due to the planar shape was exhibited in thecrystal. Since this result indicates that the planar shape and theV-shape have different π-conjugate structures, respectively, it isexpected that the compound (x) functions as a stress probe.

-   -   ¹H NMR (600 MHz, CDCl₃): δ 8.51 (dd, J=6.9, 3.3 Hz, 4H), 8.45        (s, 4H), 7.51 (dd, J=6.6, 3.0 Hz, 4H), 7.17 (s, 4H), 1.34-1.29        (m, 12H), and 1.27 (d, J=5.4 Hz, 72H) ppm; ¹³C NMR (101 MHz,        CDCl₃): δ 135.8, 133.4, 132.6, 131.6, 123.1, 127.4, 126.9,        118.4, 105.2, 103.5, 19.0, and 11.7 ppm; melting point: >200°        C.; UV-visible absorption (in CH₂Cl₂): λ_(max)=319, 410, 434,        and 461 nm; fluorescence (in CH₂Cl₂, λ_(ex)=410 nm): λ_(max)=470        and 504 nm, Φ_(F)=0.18.

Synthesis 3 of Precursor

Synthesis of Compound (y)

Tris(dibenzylidene acetone)dipalladium (44 mg, 48 μmol) and rac-BINAP(60 mg, 96 μmol) were put in a flask, and toluene (7.5 mL) was addedunder an argon atmosphere. After frozen and deaired for three times, themixture was stirred at 110 degrees Celsius for 30 minutes. After allowedto be cooled to room temperature, benzophenone-imine (0.26 mL, 1.6mmol), the compound (v) (160 mg, 0.30 mmol), and t-butoxy sodium (150mg, 1.56 mmol) were added and stirred at 110 degrees Celsius for 13hours. After allowed to be cooled to room temperature, the reactionmixture was filtered with celite, and the solvent was distilled away.The residue was purified by silica gel column chromatography (eluate:ethyl acetate/hexane/triethylamine=10/88/2), and a crude product of acompound (y) was obtained. Furthermore, the crude product wasre-precipitated with dichloromethane/hexane, and thereby the compound(y) was obtained as a yellow solid (190 mg, yield 67%).

-   -   ¹H NMR (CDCl₃, 600 MHz): δ/ppm=7.66 (d, 8H), 7.38 (t, 4H),        7.33-7.27 (m, 12H), 7.19 (t, 8H), 6.85 (d, 8H), 6.20 (s, 4H),        6.09 (4H).

Synthesis of Precursor Modified by Amino Group (Compound (z))

The compound (y) (46 mg, 50 μmol), tetrahydrofuran (3.0 mL), and 2.0 Mof hydrochloric acid (0.1 mL) were put in and stirred at roomtemperature for 3 hours. The solvent was distilled away from a reactionliquid, and a compound (z) was obtained as a light-brown solid (21 mg,10%) by filtration.

-   -   ¹H NMR (DMSO-d₆, 600 MHz): δ/ppm=0.67 (s), 6.55 (s), 3.7 (s,        broad).

Synthesis 8 of FLAP Precursor

(a) Dimethylacetylene dicarboxylate (1.0 equivalent amount) and2,3-dimethyl-1,3-butadiene (1.0 equivalent amount) were dissolved intoluene, which was stirred at 70 degrees Celsius for 18 hours. Next, DDQ(2,3-dichloro-5,6-dicyano-1,4-benzoquinone; 1.1 equivalent amount) wasadded, and the mixture was stirred at 70 degrees Celsius for 6 hours.

(b) NBS (N-bromosuccinimide; 2.2 equivalent amount), BPO (benzoylperoxide; 5 mol %), and α,α,α-trifluorotoluene were added and stirred at100 degrees Celsius for 10 hours, and thereby a compound 4 was obtained.

(c) CuI (2.0 equivalent amount), n-Bu₄NI (2.0 equivalent amount), Cs₂CO₃(2.1 equivalent amount), TMS (trimethylsilyl)acetylene (5.0 equivalentamount), and MeCN were added and stirred at 50 degrees Celsius for 20hours.

(d) AgNO₃ (10 equivalent amount) and CH₂Cl₂/acetone/H₂O were added andstirred at room temperature for 1 hour. Next, an excessive amount ofconcentrated hydrochloric acid was added, and a compound 5 was obtainedby stirring at room temperature for 1 hour.

(e) Zn (50 mol %), NiBr₂ (dme; 1,2-dimethoxyethane) (25 mol %), andTHF/H₂O were added and stirred at 60 degrees Celsius for 2 hours. Next,DDQ (4.2 equivalent amount) and toluene were added and stirred at roomtemperature for 30 minutes, and thereby a compound 6 was obtained.

(f) Br₂ (1.1 equivalent amount) and CH₂Cl₂ were and stirred at 40degrees Celsius for 2 hours. Next, DBU(1,8-diazabicyclo[5.4.0]undeca-7-ene; 10 equivalent amount) and benzenewere added and stirred at 80 degrees Celsius for 1 hour.

(g) MeB(OH)₂ (4.0 equivalent amount), K₃PO₄ (4.0 equivalent amount),PPh₃ (40 mol %), Pd(OAc)₂ (10 mol %), and THF were added and refluxedfor 24 hours.

(h) LiAlH₄ (4.5 equivalent amount) and THF were added and stirred at 60degrees Celsius for 4 hours.

(i) (COCl)₂ (4.4 equivalent amount), DMSO (8.8 equivalent amount), andCH₂Cl₂ were added and stirred at −78 degrees Celsius for 6 hours. Then,NEt₃ (35 equivalent amount) was added, and the mixture was stirred at 0degree Celsius for 2 hours.

(j) Maleimide (compound 11) (2.4 equivalent amount), PBu₃ (2.6equivalent amount), DBU (0.20 equivalent amount), and 1,2-dichloroethanewere added and stirred at 80 degrees Celsius for 40 hours, and thereby aFLAP precursor compound (FLAP2) was obtained.

Synthesis of FLAP Example 1a

Synthesis of N-(4-hydroxy-2,6-diisopropylphenyl)maleimide (Compound (I))

Under an argon atmosphere, 4-amino-3,5-diisopropylphenyl (synthesized inaccordance with a method described in Advanced Synthesis & Catalysis,2014, 356, p 460-474, 2.8 g, 14 mmol) and maleic anhydride (1.7 g, 17mmol) were dissolved in acetic acid (70 mL), which was stirred at 110degrees Celsius for 14 hours. Then, after the reaction mixture wasdiluted with acetic acid, extracted by using a sodium hydrogen carbonatesolution and a saturated saline solution, and dehydrated by passing theorganic layer through anhydrous sodium sulfate, the solvent wasdistilled away. The obtained crude product was purified by silica gelcolumn chromatography (eluate: methylene chloride/ethyl acetate=20/1)and then recrystallized by using hexane, and thereby a compound (I) wasobtained as a white solid (3.08 g, 79%). The spectrum data of thecompound (I) was as follows.

-   -   ¹H NMR (600 MHz, CDCl₃) δ (ppm) 6.87 (s, 2H), 6.69 (s, 2H) 4.80        (s, 1H), 2.56 (sept, J=6.9 Hz, 2H) and 1.13 (d, J=6.9 Hz, 12H);        ¹³C NMR (150 Mhz, CDCl₃) δ (ppm) 171.0, 157.1, 149.5, 134.4,        119.0, 111.2, 29.5 and 24.0; HR-APCI TOF-MS (m/z) found        279.1358, calcd for C₁₆H₁₉NO₃:273.1365 [M].

Synthesis ofN-(2,6-diisopropyl-4-(tetrahydropyranyloxy)phenyl)-maleimide (Compound(II))

Under an argon atmosphere, the compound (I) (3.1 g, 11 mmol) andpyridinium paratoluenesulfonate (310 mg, 1.2 mmol) were dissolved inmethylene chloride (85 mL), 3,4-dihydro-2H-pyran (2.9 mL, 33 mmol) wasadded at 0 degrees Celsius, and the mixture was stirred at roomtemperature for 12 hours. After the reaction solution with added waterwas washed with a saturated saline solution, the organic layer waspassed through anhydrous sodium sulfate for dehydration, and the solventwas distilled away. Recrystallization was performed with a mixturesolvent of methylene chloride and hexane, and thereby a compound (II)was obtained as white powder (3.86 g, 96%). The spectrum data of thecompound (II) as follows.

-   -   ¹H NMR (600 MHz, CDCl₃) δ (ppm) 6.92 (s, 2H), 6.86 (s, 2H) 5.45        (m, 1H), 3.92 (m, 1H), 3.63 (m, 1H) 2.57 (sept, J=6.9 Hz, 2H),        2.02 (m, 1H), 1.87 (m, 2H), 1.67-1.69 (m, 2H), 1.62-1.63 (m, 1H)        and 1.13 (d, J=6.9 Hz, 12H); ¹³C NMR (150 Mhz, CDCl₃) δ (ppm)        170.9, 158.7, 148.9, 134.4, 119.5, 111.2, 96.3, 61.9, 30.5,        29.5, 25.4, 24.0 and 18.7.

Synthesis Method of Compound (IV)

Under an argon atmosphere, the compound (II) (560 mg, 1.6 mmol) wasdissolved in 1,2-dichloroethane (12 mL), tributylphosphine (410 μL, 1.7mmol) was added at 0 degree Celsius, and the mixture was stirred at roomtemperature for 30 minutes. To this reaction solution,1,2-dichloroethane solution (10 mL) of a compound (III) (synthesized inaccordance with a method described in Journal of Materials Chemistry C,2017, 5, p 5248-5256, 270 mg, 0.65 mmol) was added at 0 degree Celsius,then diazabicycloundecene (20 μL, 0.13 mmol) were added. The reactionsolution was stirred at 80 degrees Celsius for 15 hours. After thereaction solution with added water was washed with a saturated salinesolution, the organic layer was passed through anhydrous sodium sulfatefor dehydration, and the solvent was distilled away. The crude productwas purified by silica gel column chromatography (eluate: methylenechloride/hexane/ethyl acetate=1/1/1), and thereby a compound (IV) wasobtained as a yellow solid (140 mg, 20%). The spectrum data of thecompound (IV) was as follows.

-   -   ¹H NMR (600 MHz, CDCl₃) δ (ppm) 8.55 (s, 4H), 8.54 (s, 4H), 7.94        (, 4H), 7.24 (s, 4H), 6.98 (s, 4H), 5.49 (m, 2H), 3.95 (m, 2H),        3.64 (m, 4H), 2.71 (sept, J=6.9 Hz, 4H), 2.04 (m, 2H), 1.87 (m,        4H), 1.71-1.70 (m, 4H), 1.60-1.62 (m, 2H) and 1.15 (d, J=6.9 Hz,        24H); ¹³C NMR (150 MHz, CDCl₃) δ (ppm) 168.1, 158.9, 148.5,        136.7, 133.4, 132.5, 132.3, 129.9, 128.6, 126.7, 120.8, 112.1,        96.4, 62.0, 30.6, 29.7, 25.5, 24.1 and 18.8 (19 peaks were        observed for 20 carbons due to partial signal coverage.)

Synthesis of Both Terminals OH Modified FLAP (Compound (V))

The compound (IV) (140 mg, 0.13 mmol) was dissolved in methylenechloride (30 mL) and methanol (10 mL), trifluoroacetic acid (2.0 mL,0.16 mmol) was added, and the mixture was stirred at room temperaturefor 4 hours. After the reaction solution with added water was washedwith a saturated saline solution, the organic layer was passed throughanhydrous sodium sulfate for dehydration, and the solvent was distilledaway. The crude product was purified by silica gel column chromatography(eluate: methylene chloride/ethyl acetate=1/1), recrystallization wasfurther performed with a mixture solvent of methylene chloride andhexane, and thereby a compound (V) was obtained as a yellow solid (110mg, 92%). The spectrum data of the compound (V) was as follows.

-   -   ¹H NMR (600 MHz, CDCl₃) δ (ppm) 8.55 (, 8H), 7.94 (s, 4H), 7.24        (s, 4H), 6.75 (s, 4H), 4.83 (s, 4H), 2.70 (sept, J=6.9 Hz, 4H)        and 1.14 (d, J=6.9 Hz, 24H); ¹³C NMR (150 MHz, DMSO-d₆) δ (ppm)        167.5, 158.6, 147.9, 136.1, 133.1, 131.9, 131.4, 130.0, 128.3,        126.6, 125.7, 118.4, 110.5, 28.6 and 23.5.

Example 1b

Synthesis of Both Terminals OH Modified FLAP (Compound (V′)) HavingSubstituent Group in Ring A

To obtain a compound (V′) that is a FLAP in which both terminals of theFLAP denoted as “FLAP2: R=Me” represented in Formula 32 are modified byOH groups as polymerizable groups, OH groups having protective groupsare introduced to both the terminals of a FLAP having a substituentgroup in the ring A by using the same method as the method representedin Formula 32 except that (a) the compound (II) represented in Formula31 (that is,N-(2,6-diisopropyl-4-(tetrahydropyranyloxy)phenyl)-maleimide) or (b) thecompound (IX) represented in Formula 33 illustrated below (that is,N-(4-(1,3-dimethoxypropanil)-2,6-diisopropylphenyl)-maleimide is usedinstead of the compound (11) represented in Formula 32 (that is,N-(2,6-diisopropylphenyl)-maleimide). The compound (V′), which is a FLAPhaving a substituent group in the ring A and modified by OH groups as apolymerizable group at both the terminals, is obtained by de-protectingthe protective groups for the obtained compound in which OH groupshaving protective groups are introduced to both the terminals of a FLAPhaving a substituent group in the ring A by using the same method as ade-protection reaction for obtaining (a) the compound (V) from thecompound (IV) represented in Formula 31 or (b) the compound (XI) fromthe compound (X) represented in Formula 33 illustrated below.

Example 2

Synthesis of 2-(4-amino-3,5-diisopropylphenyl)malonic acid Diethyl(Compound (VI))

Under an argon atmosphere, 4-iodo-2,6-diisopropylaniline (synthesized inaccordance with a method described in Dalton Transaction, 2012, 41, p6803-6812, 6.1 g, 20 mmol), copper iodide (290 mg, 1.5 mmol), cesiumcarbonate (9.8 g, 30 mmol), and 2-phenylphenol (510 mg, 3.0 mmol) weredissolved in tetrahydrofuran (20 mL), diethyl malonate (6.1 mL, 40 mmol)was added, and the mixture was stirred at 70 degrees Celsius for 24hours. After the reaction solution with added water was diluted withethyl acetate and washed with a saturated saline solution, the organiclayer was passed through anhydrous sodium sulfate for dehydration, andthe solvent was distilled away. The crude product was purified by silicagel column chromatography (eluate: methylene chloride), and a compound(VI) was obtained as a brown oily substance (4.0 g, 55%). The spectrumdata of the compound (VI) was as follows.

-   -   ¹H NMR (600 MHz, CDCl₃) δ (ppm) 7.04 (s, 2H) 4.50 (s, 1H),        4.25-4.16 (m, 4H), 3.75 (s, 2H), 2.90 (sept, J=6.9 Hz, 2H) and        1.28-1.25 (m, 18H); ¹³C NMR (150 MHz, CDCl₃) δ (ppm) 169.0,        140.4, 132.4, 124.0, 122.6, 61.6, 58.0, 28.2, 22.5 and 14.2.

Synthesis of 2-(4-amino-3,5-diisopropylphenyl)propane-1,3-diol (Compound(VII)

Under an argon atmosphere, a tetrahydrofuran solution (10 mL) of thecompound (VI) (1.5 g, 4.2 mmol) was added at 0 degree Celsius to atetrahydrofuran suspension (10 mL) of lithium aluminum hydride (400 mg,10 mmol), and the mixture was stirred at room temperature for 4 hours.After a sodium sulfate solution was added, the suspension was filteredto remove aluminum salt, the filtrate was passed through silica gelcolumn (eluate: ethyl acetate), and a crude product was obtained.Recrystallization was performed with a mixture solvent of methylenechloride and hexane, and thereby a compound (VII) was obtained as awhite solid (910 mg, 87%). The spectrum data of the compound (VII) wasas follows.

-   -   ¹H NMR (600 MHz, CDCl₃) δ (ppm) 6.87 (s, 2H), 3.98-3.94 (m, 2H),        3.91-3.88 (m, 2H), 3.70 (s, 2H), 3.03 (tt, J=7.8, 5.4 Hz, 1H),        2.92 (sept, J=6.6 Hz, 2H), 1.92 (t, J=5.4 Hz, 2H) and 1.26 (d,        J=6.6 Hz), 12H); ¹³C NMR (150 MHz, CDCl₃) δ (ppm) 139.4, 133.0,        128.7, 122.4, 66.5, 49.7, 28.1 and 22.5; HR-APCI TOF-MS (m/z)        found 252.1968, calcd for C₁₅H₂₅NO₂: 252.1958 [M+H]⁺.

Synthesis of 4-(1,3-dimethoxypropanil)-2,6-diisopropylaniline (Compound(VIII))

Under an argon atmosphere, a tetrahydrofuran solution (4.5 mL) of thecompound (VI) (900 mg, 3.6 mmol) was added at 0 degree Celsius to sodiumhydrogenide (60%, dispersed in fluid paraffin, 400 mg, 10 mmol) andtetrahydrofuran suspension (9.0 mL) of methyl iodide (450 μL, 7.2 mmol),and the mixture was stirred at room temperature for 1 hour. After thereaction solution was diluted by ethyl acetate (20 mL), the solvent wasdistilled away, and a crude product was obtained. The crude product waspurified by silica gel column chromatography (eluate: methylenechloride/hexane/ether=1/1/1), a compound (VIII) was obtained as a brownoily substance (930 mg, 93%). The spectrum data of the compound (VIII)was as follows.

-   -   ¹H NMR (600 MHz, CDCl₃) δ (ppm) 6.92 (s, 2H), 3.63 (dd, 9.2, 6.8        Hz, 2H), 3.57 (dd, J=9.7, 6.4 Hz, 2H), 3.39 (s, 6H), 3.06 (tt,        J=9.2, 6.4 Hz, 1H), 2.91 (sept, J=6.9 Hz, 2H), and 1.27 (d,        J=6.9 Hz, 12H): ¹³C NMR (150 MHz, CDCl₃) δ (ppm) 139.1, 132.4,        130.5, 122.4, 74.5, 59.0, 45.8, 28.1 and 22.5; HR-APCI TOF-MS        (m/z) found 280.2271, calcd for C₁₇H₂₉NO₂: 280.2271 [M+H]⁺.

Synthesis ofN-(4-(1,3-dimethoxypropanil)-2,6-diisopropylphenyl)-maleimide (Compound(IX))

Under an argon atmosphere, the compound (VIII) (1.0 g, 3.7 mmol) andmaleic anhydride (720 mg, 7.4 mmol) were dissolved in acetic acid (2.2mL), which was stirred at room temperature for 10 hours. Then, sulfuricacid (95%, 370 μL) and acetic anhydride (180 μL) were added to thereaction solution, which was heated to 60 degrees Celsius and stirredfor 10 hours. After the reaction solution with added water was dilutedwith ethyl acetate, and washed with a saturated saline solution, theorganic layer was passed through anhydrous sodium sulfate fordehydration, and the solvent was distilled away. The crude product waspurified by silica gel column chromatography (eluate: methylenechloride/ether=6/1), and a compound (IX) was obtained as a white solid(1.1 g, 80%). The spectrum data of the compound (IX) was as follows.)

-   -   ¹H NMR (600 MHz, CDCl₃) δ (ppm) 7.12 (s, 2H), 6.88 (s, 2H),        3.67-3.64 (m, 2H), 3.63-3.60 (m, 2H), 3.35 (s, 6H), 3.13 (tt,        J==7.2, 6.0 Hz, 1H), 2.59 (sept, J=6.9 Hz, 2H) and 1.15 (d,        J=6.9 Hz, 12H); ¹³C NMR (150 MHz, CDCl₃) δ (ppm) 170.8, 147.2,        142.9, 134.4, 124.5, 124.0, 74.0, 59.0, 46.4, 29.4, and 24.1;        HR-APCI TOF-MS (m/z) found 359.2096, calcd for C₂₁H₂₉NO₄:        359.2097 [M+H]⁺.

Synthesis of Compound (X)

Under an argon atmosphere, the compound (IX) (680 mg, 1.90 mmol) wasdissolved in 1,2-dichloroethane (30 mL), tributylphosphine (510 μL, 2.1mmol) was added at 0 degree Celsius, and the mixture was stirred at roomtemperature for 30 minutes. Then, a 1,2-dichloroethane solution (15 mL)of the compound (III) (330 mg, 0.79 mmol) was added to the reactionsolution at 0 degree Celsius, diazabicycloundecene (24 μL, 0.16 mmol)was added, and the mixture was stirred at 80 degrees Celsius for 12hours. The reaction solution with added water was divided by a saturatedsaline solution, the organic layer was passed through anhydrous sodiumsulfate for dehydration, the solvent was distilled away, and a crudeproduct was obtained. The crude product was purified by silica gelcolumn chromatography (eluate: methylene chloride/ether=5/1), and acompound (X) was obtained as a yellow solid (208 mg, 25%). The spectrumdata of the compound (X) was as follows.

-   -   ¹H NMR (600 MHz, CDCl₃) δ (ppm) 8.55 (s, 4H+4H), 7.94 (s, 4H),        7.24 (s, 4H), 7.16 (s, 4H), 3.70-3.67 (m, 4H), 3.66-3.63 (m,        4H), 3.37 (s, 12H), 3.16 (tt, J=7.2, 6.0 Hz, 2H), 2.72 (sept,        J=6.8 Hz, 4H) and 1.15 (d, J=6.8 Hz, 24H); ¹³C NMR (150 MHz,        CDCl₃) δ (ppm) 167.9, 146.7, 142.8, 136.6, 133.4, 132.4, 132.2,        129.8, 128.4, 126.64, 126.50, 125.9, 123.8, 76.9, 59.1, 46.4,        29.6, and 24.0.

Synthesis of Compound (XI)

Under an argon atmosphere, the compound (X) (170 mg, 0.16 mmol) wasdissolved in methylene chloride (12 mL), a methylene chloride solutionof boron tribromide (1.0 M, 2.48 mL) was added at −78 degrees Celsius,and the mixture was stirred for 4 hours while gradually heated back toroom temperature. The reaction solution with added water was divided bya saturated saline solution, the organic layer was passed throughanhydrous sodium sulfate for dehydration, the solvent was distilledaway, and a crude product was obtained. The crude product was purifiedby silica gel column chromatography (eluate: ether), and a compound (XI)was obtained as a yellow solid (21 mg, 13%). The spectrum data of thecompound (XI) was as follows.

-   -   ¹N MR (600 MHz, CDCl₃) δ (ppm) 8.55 (m, 8H), 7.94 (s, 4H), 7.24        (s, 4H), 7.16 (s, 4H), 3.70-3.67 (m, 4H), 3.66-3.63 (m, 4H),        3.37 (s, 12H), 3.16 (tt, J=7.2, 6.0 Hz, 2H), 2.72 (sept, J=6.8        Hz, 4H) and 1.15 (d, J=6.8 Hz, 24H); ¹³C NMR (150 MHz, CDCl₃) δ        (ppm) 167.9, 146.7, 142.8, 136.6, 133.4, 132.4, 132.2, 129.8,        128.4, 126.64, 126.59, 125.9, 123.8, 76.9, 59.1, 46.4, 29.5, and        24.0.

Example 3

Synthesis ofN-(2,6-diisopropylphenyl)-1,6-bis(4-methoxyphenoxy)-9-bromoperilene-3,4-dicarboxymide(Compound (XII))

N-(2,6-diisopropylphenyl)-1,6,9-tribromoperylene-3,4-dicarboxymide(synthesized in accordance with a method described in Journal ofMaterials Chemistry, 1998, 8, p 2357-2369, 0.50 g, 0.70 mmol), potassiumcarbonate (K₂CO₃; 0.21 g, 1.5 mmol), 4-methoxyphenol (0.16 g, 1.3 mmol)were put in a Schlenk, dissolved in N-methyl-2-pyrrolidone (15 mL), andstirred at 80 degrees Celsius for 3.5 hours under a nitrogen atmosphere.The reaction liquid was cooled back to room temperature and added to amixture liquid of concentrated hydrochloric acid (15 mL) and water (30mL). The deposited precipitation was filtered and dried and thenpurified by silica gel column chromatography (eluate:hexane/dichloromethane=1/2, v/v), and thereby a compound (XII) wasobtained as a red solid (0.18 g, 31%). The spectrum data of the compound(XII) was as follows.

-   -   ¹H NMR (CDCl₃, 600 MHz): δ9.40 (dd, J=7.8 Hz, 0.9 Hz, 1H), 9.17        (d, J=8.4 Hz, 1H), 8.35 (dd, J=7.8 Hz, J=0.9 Hz, 1H) 8.25 (s,        1H), 8.24 (s, 1H), 7.90 (d, J=8.4 Hz, 1H), 7.71 (t, J=8.4 Hz,        1H), 7.43 (t, J=7.8 Hz, 1H), 7.28 (d, J=8.4 Hz, 1H) 7.10-7.07        (m, 4H), 6.95-6.93 (m, 4H), 3.82 (s, 6H), 2.70-2.67 (m, 2H),        1.12 (d, J=6.8 Hz, 12H) ¹³C NMR (CDCl₃, 150 MHz): δ 163.26,        163.24, 156.76, 156.74, 154.68, 154.60, 149.15, 149.07, 145.78,        132.18, 131.65, 131.14, 131.08, 130.81, 129.55, 124.43, 129.40,        128.80, 128.28, 127.96, 127.78, 126.24, 126.12, 125.43, 124.03,        123.70, 122.59, 122.78, 122.03, 122.00, 120.56, 120.54, 115.62,        55.88, 29.23, 24.14.

Synthesis of Compound (XIII)

N-(2,6-diisopropylphenyl)-1,6-bis(4-methoxyphenoxy)-9-bromoperylene-3,4-dicarboxymide(0.18 g, 0.22 mmol), bispinacolate diborone ((BPin) 2; 90 mg, 0.35mmol), potassium acetate (70 mg, 0.67 mmol), and[1,1′-bis(diphenylphosphino)ferrocene]palladium(II) dichloride(PdCl2(dppf); 10 mg, 13 μmol) were dried in vacuum in a Schlenk,1,4-dioxane (7 mL) was added and then frozen and dehydrated. Then,stirring was performed at 70 degrees Celsius for 24 hours under anitrogen atmosphere. The reaction solution was allowed to be cooled tobe at room temperature, and the solvent was distilled away. The residuewas purified by silica gel column chromatography (eluate:hexane/dichloromethane=1/2, v/v), and thereby a compound (XIII) wasobtained as a red solid (0.15 g, 82%). The spectrum data of the compound(XIII) was as follows.

-   -   ¹H NMR (CDCl₃, 600 MHz): δ 9.36 (d, J=7.8 Hz, 1H), 9.32 (d,        J=8.4 HZ, 1H), 8.92 (d, J=8.4 Hz, 1H), 8.300 (s, 1H), 8.298 (s,        1H), 8.22 (J=7.8 Hz, 1H), 7.67 (t, J=8.4 Hz, 1H), 7.45 (t, J=7.8        Hz, 1H), 7.30 (d, J=7.8 Hz, 2H), 7.10-7.07 (m, 4H), 6.94-6.92        (m, 4H), 3.82 (s, 6H), 2.75-2.72 (m, 2H), 1.46 (s, 12H), 1.16        (d, J=6.8 Hz, 12H); ¹³C NMR (CDCl₃, 150 MHz): δ163.30, 156.48,        156.45, 154.50, 154.21, 149.41, 145.78, 137.19, 127.59, 127.45,        127.09, 127.08, 124.08, 124.02, 123.98, 123.00, 121.97, 121.39,        120.33, 120.13, 115.48, 84.19, 55.82, 29.18, 25.08, 24.12.

Synthesis of Compound (XV)

The compound (XIII) (0.15 g, 0.18 mmol), the compound (f) (34 mg, 0.078mmol), palladium (II) acetate (1.9 mg, 8.4 μmol),2-cyclohexylphosphino-2′,4′,6′-triisopropyl biphenyl (XPhos; 7.8 mg, 16μmol), tripotassium phosphate (K₃PO₄; 84 mg, 0.40 mmol), and water (25μL) were dissolved in tetrahydrofuran (6.0 mL) in a Schlenk and frozenand dehydrated. Then, stirring was performed at 60 degrees Celsiusovernight under a nitrogen atmosphere. The reaction solution was allowedto be cooled to be at room temperature, and the solvent was distilledaway. The residue was purified by silica gel column chromatography(eluate: dichloromethane), and thereby an isomeric mixture (XIV) wasobtained as a red solid crude product.

The obtained isomeric mixture (XIV) and PdCl₂(PCy₃)₂ (11 mg, 15 μmol)were dried in vacuum in the Schlenk. 1,8-diazabicyclo[5.4.0]-7-undecene(53 μL, 0.35 mmol) and dimethylacetamide (2.7 mL) were added anddehydrated in vacuum. The reaction liquid was stirred at 140 degreesCelsius for 22 hours under a nitrogen atmosphere. The reaction liquidwas allowed to be cooled to room temperature, methanol (20 mL) was thenadded, and the deposited precipitation was filtered. After the obtainedprecipitation was purified by silica gel column chromatography (eluate:dichloromethane) and recycle HPLC (eluate: chloroform), reprecipitationwas further performed with a chloroform/methanol mixture solvent, afiltered solid was washed with chloroform, and thereby a compound (XV)was obtained as a blue solid (2.2 mg, 1.6%). The spectrum data of thecompound (XV) was as follows.

-   -   ¹H NMR (CDCl₃, 600 MHz) δ 9.52 (d, J=8.4 Hz, 4H), 8.26 (s, 4H),        8.17 (s, 4H), 8.05 (d, J=8.4 Hz, 4H), 7.71 (s, 4H), 7.42 (d,        J=8.4 Hz, 2H), 7.27 (d, J=7.8 Hz, 4H), 7.13-7.11 (m, 12H), 6.94        (d, J=9.0 Hz, 8H), 3.82 (s, 12H), 2.70-2.67 (m, 4H), 1.11 (d,        J=6.8 Hz, 24H).

Synthesis of Compound (XVI)

The compound (XV) (5.0 mg, 2.8 μmol) was dissolved in dehydrateddichloromethane (2.5 mL), methylene chloride solution of borontribromide (1 M, 0.10 mL, 0.10 mmol) was added under a nitrogenatmosphere, and the mixture was stirred at room temperature for 2 hours.After methylene chloride was evaporated by nitrogen flow, methanol (2.5mL) and water (2.5 mL) were added. The obtained suspension was heatedfor 1 minute and then allowed to be cooled, filtered out by using water,and dried in vacuum, and thereby a compound (XVI) was obtained as aviolet solid (4.3 mg, 90%). The spectrum data of the compound (XVI) wasas follows.

-   -   ¹H NMR (DMSO-d₆, at 120° C., 600 MHz): δ 9.52-9.51 (m, 4H), 9.11        (br, 4H), 8.42 (br, 4H), 8.29-8.28 (m, 4H), 8.10 (br, 4H), 7.84        (br, 4H), 7.43-7.39 (m, 2H), 7.29-7.27 (m, 4H), 7.15-7.13 (m,        12H), 6.91-6.89 (m, 8H), 2.67-2.65 (m, 4H), 1.06-1.04 (m, 24H).

Example 4

[Synthesis of Polymer Film in which FLAP is Put in Cross-Linkage Pointof Polyurethane]

After a small amount of the compound (XVI) synthesized in Example 3 andpolytetrahydrofuran (Mn up to 650, 2.09 g) were dried in vacuum in aflask and dissolved while adding 4.1 mL of dehydrated dimethylformamide.Furthermore, after hexamethylene diisocyanate (0.78 mg, 4.86 mmol) andtriethanolamine (0.15 mL, 148 mg, 1.12 mmol) were added and stirred,dibutyltin di-laurate (7 drops) was added, and the mixture was stirredat room temperature for 5 minutes. The obtained viscous liquid mixturewas poured into a polytetrafluoroethylene mold shaped in a film testpiece, left at room temperature for 2 days to develop a polymerizationreaction under a nitrogen atmosphere. The mold was then dried in vacuumovernight to fabricate film-like polyurethane. The film test piece withthe mold was immersed and washed in a 1,4-dioxane solvent for 1 day, thefilm test piece removed from the mold was taken out from the solvent andagain dried in vacuum overnight, and thereby a red light-emitting FLAPcross-linkage polyurethane film was obtained.

Confirmation of Optical Stability Example 5

In experiments for optical stability, the compound (k) was dissolved inan undehydrated dichloromethane solvent to obtain a solution with theinitial concentration of 24 μM. This solution was put in 1 cm squarequartz cell for fluorescence measurement, and a lid was put thereon.

Next, a UV-LED having a wavelength of 365 nm is fixed at a place apartby 10 cm from the quartz cell, and a solution in the quartz cell wascontinuously irradiated with UV light (irradiation intensity: 40 mW/cm²)while being stirred. The fluorescence spectrum was measured every 10minutes (excitation wavelength: 365 nm), and the rate of fluorescenceattenuation due to photodegradation was measured. The measurement resultwas illustrated in FIG. 5.

Comparative Example 1

The fluorescence spectrum was measured by the same method as in Example5 except that a cyclooctatetraene condensed-ring anthracene imide dimer(“compound 3d” described in Chem. Eur. J. 2014, 20, 2193-2200. See FIG.5 for the structure) was in a dichloromethane solution with the initialconcentration of 12 μM. FIG. 5 illustrates the result.

As illustrated in FIG. 5, while the fluorescence intensity wassignificantly attenuated by two-hour UV irradiation in Comparativeexample 1, a high fluorescence intensity was still maintained in Example5. It was revealed from the above results that the novel FLAP accordingto the embodiment improved optical stability compared to theconventional compound.

Example 6

Instead of the experiment using the solvent of Example 5, the compound(k) was doped in a polymer thin film (Zeonex, film thickness: around 100nm) at a low concentration of 1 nM to 100 nM, and the rate ofattenuation of fluorescence when irradiated with light at an intensityof 36 W/cm² was measured. FIG. 6 illustrates the result.

Comparative Example 2

Evaluation was made by the same method as that in Example 6 except thata cyclooctatetraene condensed-ring anthracene imide dimer (the compoundA1 of Example 1 in Patent Literature 3 described above) was used insteadof the compound (k). FIG. 7 illustrates the result.

First, in Comparative example 2, after light irradiation is started atan intensity of 36 W/cm², substantially all the bright spots disappearedin 0.5 seconds, as illustrated in FIG. 7. On the other hand, in Example6, clear bright spots were observed even after 10-second irradiation, asillustrated in FIG. 6. Furthermore, a fluorescence spectrum at eachbright spot was measured, it was found that the shape thereof matchedthat of the fluorescence spectrum in the toluene solution, and thisrevealed that sufficient optical stability and fluorescence quantumyield for single-molecule fluorescence imaging were provided.

[Example of Synthesis of Intermediate Used for Manufacturing FLAPPrecursor]

After t-BuOK (423 mg, 3.77 mmol) was added to a THF solution of(5-bromo-2-fluorobenzyl)triphenylphosphonium bromide (2.0 g, 3.77 mmol)and the mixture was stirred at 0 degree Celsius for 30 minutes,5-bromo-2-hydroxybenzaldehyde (51.7 mg, 1.72 mmol) was added, and themixture was stirred at 25 degrees Celsius for 16 hours. After dilutehydrochloride acid was added to the reaction solution to stop thereaction, the organic layer divided by using dichloromethane wasextracted to distill the solvent. The residue was purified by silica gelcolumn chromatography by using dichloromethane/hexane (1:1 by volume) asa developing solvent. As a result, in addition to the primary product(E)-4-bromo-2-(5-bromo-2-fluorostyryl)phenol (430 mg, yield 66%), theintended 2,8-dibromodibenzo[b,f]oxepine having a seven-membered ringstructure was obtained (110 mg, yield 18%). The spectrum data was asfollows.

-   -   ¹H NMR: δ/ppm (in heavy chloroform) 7.39 (dd, J=8.7, 2.3 Hz,        2H), 7.29 (d, J=2.3 Hz, 2H), 7.02 (d, J=8.7 Hz, 2H), 6.63 (s,        2H). ¹³C NMR: δ/ppm. (in heavy chloroform) 156.26, 132.92,        132.15, 132.08, 130.04, 123.10, 118.04.

Note that the spectrum data of the compound of(E)-4-bromo-2-(5-bromo-2-fluorostyryl)phenol was as follows.

-   -   ¹H NMR: δ/ppm (in heavy chloroform) 7.74 (dd, 6.6, 2.4 Hz, 1H),        7.69 (d, J=2.4 Hz, 1H), 7.34 (d, J=16.5 Hz, 1H), 7.34 (ddd,        J=4.4, 4.2, 2.4 Hz, 1H), 7.26 (dd, 8.4, 2.4 Hz, 1H), 7.18 (d,        J=16.5 Hz, 1H), 6.97 (dd, J=9.9, 8.4 Hz, 1H), 6.71 (d, J=7.8 Hz,        1H), 4.92 (s, 1H).

After a THF solution of 2,8-dibromodibenzo[b,f]oxepine (100 mg, 0.284mmol) was cooled to −98 degrees Celsius, an n-hexane solution (0.18mol/L, 1.6 mL, 0.29 mmol) of n-BuLi was added, and the mixture wasstirred at −98 degrees Celsius for 30 minutes, dimethylformamide (0.22mL, 2.8 mmol) was added, and the temperature was increased up to 25degrees Celsius in 30 minutes. After water was added to the reactionsolution to stop the reaction, the organic layer divided by usingdichloromethane was extracted, and the solvent was distilled away. Theresidue was purified by silica gel column chromatography by usingdichloromethane/hexane (4:1 by volume) as a developing solvent. As aresult, 8-bromodibenzo[b,f]oxepine-2-carbaldehyde was obtained (75.7 mg,yield 88%). The spectrum data was as follows.

-   -   ¹H NMR (in heavy chloroform) δ/ppm 9.91 (s, 1H), 7.83 (dd,        J=8.4, 1.8 Hz, 1H), 7.69 (1H), 7.69 (d, J=2.4 Hz, 1H), 7.41 (dd,        J=8.4, 2.4 Hz, 1H), 7.30 (d, J=1.8 Hz, 1H), 7.28 ((d, J=8.4 Hz,        1H), 7.05 (d, J=8.4 Hz, 1H), 6.75 (d, J=11.5 Hz, 1H), 6.66 (d,        J=11.5 Hz, 1H) ¹³C NMR: δ/ppm (in heavy chloroform) 190.76,        162.01, 155.83, 133.80, 133.09, 132.22, 132.10, 131.81, 131.36,        131.05, 130.38, 130.13, 121.29, 122.47, 118.41.

It is possible to synthesize dibenzo[b,f]oxepine-2,8-dicarbaldehyde byusing two equivalent amount of n-BuLi to activate DMF in the same manneras the above reaction. Furthermore, by activating NaBH₄ to reduce andtransform aldehyde into alcohol, it is possible to obtaindibenzo[b,f]oxepine-2,8-diyldimethanol having a hydroxy group that is apolymerizable group. Further, it is possible to synthesize(10-methyldibenzo[b,f]oxepine-2,8-diyl)dimethanol in which a methylgroup is introduced to the center seven-membered ring by applying thesame chemical transformation as in the case of a FLAP having the centereight-membered ring structure. An intermediate used for manufacturing aFLAP precursor is obtained in such a way. Next, a substituent group usedfor forming a substructure that inhibits aggregation and, if necessary,a substituent group used for forming a substructure having apolymerizability are introduced to the intermediate, and thereby theFLAP precursor is obtained. Note that the method of obtainingpolyurethane from a monomer having hydroxy groups at both terminals isin accordance with the case of the FLAP having the center eight-memberedring structure.

Furthermore, as the method for introducing a polymerizable group,another method below may be employed.

After an ethylene glycol solution (1.0 mL) of2,8-dibromodibenzo[b,f]oxepine (78.0 mg, 0.221 mmol), copper(II)chloride (1.5 mg, 0.011 mmol), and potassium carbonate (91.2 mg, 0.659mmol) was stirred at 130 degrees Celsius for 5 hours, water was added tothe reaction solution to stop the reaction, the organic layer divided byusing dichloromethane was extracted, and the solvent was distilled away.The residue was purified by silica gel column chromatography by usingdichloromethane/ethyl acetate (1:1 by volume) as a developing solvent.As a result, 2,2′-(dibenzo[b,f]oxepine-2,8-diylbis(oxy)) bis(ethan-1-ol) was obtained (30.0 mg, yield 43%). The spectrum data was asfollows.

-   -   ¹H NMR: (in heavy chloroform) δ/ppm 7.09 (d, J=9.2 Hz, 2H), 6.84        (dd, J=9.2, 2.8 Hz, 2H), 6.70 (d, J=2.8 Hz, 2H), 6.67 (s, 2H),        7.05 (d, J=8.4 Hz, 1H), 6.75 (d, J=11.5 Hz, 1H), 6.66 (d, J=11.5        Hz, 1H), 4.04 (dd, J=4.8, 4.2 Hz, 4H), 3.94 (m, 4H), 1.95 (dd,        J=6.6, 6.0 Hz, 2H). ¹³C NMR: δ/ppm (in heavy chloroform) 155.64,        151.92, 131.23, 130.43, 122.01, 115.99, 114.77, 69.89, 61.62.

INDUSTRIAL APPLICABILITY

With a use of the compound illustrated in the embodiments, a moleculehaving higher fluorescence quantum yield and higher optical stabilitythan the conventional FLAP can be obtained. Therefore, the compound anda polymer compound containing the compound can be used as a material formeasurement with a viscosity probe or the like.

1. A compound represented by a following general Formula (1):

wherein in general Formula (1), A denotes a seven-membered ring oreight-membered ring structure that may have a substituent group andforms a conjugated system with a benzene ring bound to A, Y¹ and Y² eachdenote, independently, a substituent group selected from a halogen atom,an aliphatic hydrocarbon group with 1-20 carbons that may have asubstituent group, an aryl group with 6-20 carbons that may have asubstituent group, an alkoxy group with 1-10 carbons that may have asubstituent group, an cyano group, and a heterocyclic compound grouphaving 5-8 atoms forming a ring, and when a plurality of substituentgroups Y¹ and Y² are provided, respective substituent groups may be thesame as each other or may be different from each other, a1 denotes thenumber of the substituent groups Y¹, and a2 denotes the number of thesubstituent groups Y², Y³ denotes a substituent group selected from ahalogen atom, an alkyl group with 1-20 carbons that may have asubstituent group, an alkynyl group with 2-20 carbons that may have asubstituent group, an aryl group with 6-20 carbons that may have asubstituent group, an alkoxy group with 1-10 carbons that may have asubstituent group, a carboxylic acid ester group with 2-20 carbons thatmay have a substituent group, a carboxyl group, a hydroxyl group, and acyano group, when a plurality of substituent groups Y³ are provided,respective substituent groups may be the same as each other or may bedifferent from each other, b denotes the number of the substituentgroups Y³, m and n each denote, independently, an integer greater thanor equal to 0 and less than or equal to 3, when m is an integer greaterthan or equal to 1 and less than or equal to 3, Y¹ may be substitutedwith a structure portion defined by m, and similarly, when n is aninteger greater than or equal to 1 and less than or equal to 3, Y² maybe substituted with a structure portion defined by n, and B¹ and B² eachdenote, independently, any of the structures represented by generalFormulas (2-1) to (2-3):

wherein in general Formulas (2-1) to (2-3), C¹ denotes a structurecontaining a cyclic hydrocarbon compound, C² and C³ each denote astructure containing a cyclic hydrocarbon compound but may have nostructure containing a cyclic hydrocarbon compound, and when C² and C³have no structure containing a cyclic hydrocarbon compound, D², D³, E²,and E³ are arranged in a framework of a compound represented by generalFormula (1), D¹, D², and D³ each denote a substructure that inhibitsaggregation, E², and E³ each denote a polymerizable substructure, Z¹each denote, independently, a substituent group selected from a hydrogenatom, a halogen atom, an alkyl group with 1-20 carbons that may have asubstituent group, an alkynyl group with 2-20 carbons that may have asubstituent group, an aryl group with 6-20 carbons that may have asubstituent group, an alkoxy group with 1-10 carbons that may have asubstituent group, and a cyano group and may form a ring with C¹, andwhen a plurality of substituent groups Z¹ are provided, respectivesubstituent groups may be the same as each other or may be differentfrom each other, c denotes the number of substituent groups Z¹, and Z²and Z³ each denote, independently, a substituent group selected from ahydrogen atom, a halogen atom, an alkyl group with 1-20 carbons that mayhave a substituent group, an alkynyl group with 2-20 carbons that mayhave a substituent group, an aryl group with 6-20 carbons that may havea substituent group, an alkoxy group with 1-10 carbons that may have asubstituent group, and a cyano group, and Z² and Z³ may each form a ringwith C², independently.
 2. The compound according to claim 1, wherein inthe general Formula (1), the A is represented by general Formula (3) or(4):

wherein in general Formula (4), Q denotes an O atom, an S atom, a Seatom, or an N atom or a P atom having an alkyl group as a substituentgroup.
 3. The compound according to claim 1, wherein in the generalFormula (1), the B¹ and B² have any structure of general Formulas (5-1)to (5-3):

wherein Z⁴ in general Formula (5-2) is the same as the Z² and Z³.
 4. Thecompound according to claim 1, wherein the E¹, E², and E³ each denote apolymerizable substituent group.
 5. The compound according to claim 1,wherein the D¹, D², and D³ have any of following structures:

wherein R₁ to R₇ each denote H, a linear, branched, or cyclic alkylgroup with 1-20 carbons, an aryl group with 6-20 carbons, F, Cl, Br, I,CF₃, CCl₃, CN, or OCH₃, and R₁ to R₇ may be the same or different. 6.The compound according to claim 1, wherein the E¹, E², and E³ are any ofthe Formulas (E-1) to (E-18):

wherein in the Formulas (E-12) and (E-13), X denotes amide or ester butmay not be included, R₁ in the Formulas (E-12) and (E-13) denotes H, alinear, branched, or cyclic alkyl group with 1-20 carbons, an aryl groupwith 6-20 carbons, F, Cl, Br, I, CF₃, CN, or OCH₂, R in Formulas (E-1)to (E-18) denotes a linear, branched, or cyclic alkyl group with 1-20carbons or an aryl group with 6-20 carbons, R in Formulas (E-1) to(E-11) may not be included, and each filled circle represents D¹, D², orD³.
 7. The compound according to claim 3, wherein in the general Formula(1), the B¹ and B² have any of structures of the general Formulas (5-1)and (5-2).
 8. The compound according to claim 3, wherein in the generalFormula (1), the B¹ and B² have a structure of the general Formula(5-3), and wherein m and n of a compound represented by the generalFormula (1) are 0 or
 3. 9. The compound according to claim 1, wherein inthe general Formula (1), the a1 denotes an integer of 0 to 3 when m is0, and denotes an integer that Y¹ can be substituted in accordance withthe number 0 to m when m is an integer greater than or equal to 1 andless than or equal to 3, the a2 denotes an integer of 0 to 3 when n is0, and denotes an integer that Y² can be substituted in accordance withthe number 0 to n when n is an integer greater than or equal to 1 andless than or equal to 3, and the b denotes an integer greater than orequal to 0 and less than or equal to 4,
 10. The compound according toclaim 2, wherein in the general Formula (1), the A is the generalFormula (4).
 11. The compound according to claim 1, wherein in thegeneral Formula (1), the b is an integer greater than or equal to 1 andless than or equal to
 4. 12. A polymer compound made by polymerizing thecompound described in claim
 1. 13. The polymer compound according toclaim 12, wherein the compound is bound to the polymer compound via aurethane binding in the polymer compound.
 14. The polymer compoundaccording to claim 12 further comprising, in a main chain of the polymercompound, a chemical structure included in the compound.
 15. The polymercompound according to claim 12 further comprising a cross-linked sitemade of a chemical structure included in the compound.
 16. The compoundaccording to claim 2, wherein in the general Formula (1), the B¹ and B²have any structure of general Formulas (5-1) to (5-3):

wherein Z⁴ in general Formula (5-2) is the same as the Z² and Z³. 17.The compound according to claim 2, wherein the D¹, D², and D³ have anyof following structures:

wherein R₁ to R₇ each denote H, a linear, branched, or cyclic alkylgroup with 1-20 carbons, an aryl group with 6-20 carbons, F, Cl, Br, I,CF₃, CCl₃, CN, or OCH₃, and R₁ to R₇ may be the same or different. 18.The compound according to claim 3, wherein the D¹, D², and D³ have anyof following structures:

wherein R₁ to R₇ each denote H, a linear, branched, or cyclic alkylgroup with 1-20 carbons, an aryl group with 6-20 carbons, F, Cl, Br, I,CF₃, CCl₃, CN, or OCH₃, and R₁ to R₇ may be the same or different. 19.The compound according to claim 2, wherein the E¹, E², and E³ are any ofthe Formulas (E-1) to (E-18):

wherein in the Formulas (E-12) and (E-13), X denotes amide or ester butmay not be included, R₁ in the Formulas (E-12) and (E-13) denotes H, alinear, branched, or cyclic alkyl group with 1-20 carbons, an aryl groupwith 6-20 carbons, F, Cl, Br, I, CF₃, CCl₃, CN, or OCH₃, R in Formulas(E-1) to (E-18) denotes a linear, branched, or cyclic alkyl group with1-20 carbons or an aryl group with 6-20 carbons, R in Formulas (E-1) to(E-11) may not be included, and each filled circle represents D¹, D², orD³.
 20. The compound according to claim 3, wherein the E¹, E², and E³are any of the Formulas (E-1) to (E-18):

wherein in the Formulas (E-12) and (E-13), X denotes amide or ester butmay not be included, R₁ in the Formulas (E-12) and (E-13) denotes H, alinear, branched, or cyclic alkyl group with 1-20 carbons, an aryl groupwith 6-20 carbons, F, Cl, Br, I, CF₃, CCl₃, CN, or OCH₃, R in Formulas(E-1) to (E-18) denotes a linear, branched, or cyclic alkyl group with1-20 carbons or an aryl group with 6-20 carbons, R in Formulas (E-1) to(E-11) may not be included, and each filled circle represents D¹, D², orD₃.